Compositions formed from hydroxyaluminoxane and their use as catalyst components

ABSTRACT

Surprisingly stable olefin polymerization co-catalysts formed from hydroxyaluminoxanes are revealed. In one embodiment of the invention, a solid composition of matter is formed from a hydroxyaluminoxane and a treating agent, whereby the rate of OH-decay for the solid composition is reduced as compared to that of the hydroxyaluminoxane. Processes for converting a hydroxyaluminoxane into a such a solid composition of matter, supported catalysts formed from such solid compositions of matter, as well as methods of their use, are described.

REFERENCE TO RELATED APPLICATIONS

[0001] This is a continuation-in-part of prior co-pending U.S. patentapplication Ser. No. 09/655,218, filed Sep. 5, 2000 and incorporatedherein by reference, which is a continuation-in-part of U.S. patentapplication Ser. No. 09/177,736, filed on Oct. 23, 1998, now U.S. Pat.No. 6,160,145, incorporated herein by reference. This application mayalso be considered related to U.S. patent application Ser. No. ______,co-filed herewith (Attny. Docket No. OR-7067-C).

TECHNICAL FIELD

[0002] This invention relates to novel compositions of matter which arehighly effective as catalyst components, and to the preparation and useof such compositions.

BACKGROUND

[0003] Partially hydrolyzed aluminum alkyl compounds known asaluminoxanes (a.k.a. alumoxanes) are effective in activatingmetallocenes for polymerization ofolefins. Activating effects of waterin such systems were initially noted by Reichert, et al. (1973) andBreslow, et al. (1975), and extended to trimethylaluminum-based systemsby Sinn, Kaminsky, et al. (1976). Subsequentresearchby Sinn and Kaminskydemonstratedthatthis activation was due to formation ofmethylaluminoxane from partial hydrolysis of trimethylaluminum presentin the system. Methylaluminoxane (a.k.a. methylalumoxane) has become thealuminum co-catalyst of choice in the industry.

[0004] Subsequent to the above original discoveries in this field,considerable worldwide effort has been devoted to improving theeffectiveness of catalyst systems based on use of aluminoxanesormodified aluminoxanes forpolymerization ofolefins and relatedunsaturated monomers.

[0005] Representative of many patents in the field of aluminoxane usagein forming olefin polymerization catalyst systems with suitable metalcompounds is U.S. Pat. No. 5,324,800 to Welborn et al. which claims anoriginal filing date in 1983. This patent describes olefinpolymerization catalysts made from metallocenes of a metal of Groups 4b,5b, or 6b, and a cyclic or linear C1-C5 alkylaluminoxane. The cyclic andthe linear aluminoxanes are depicted, respectively, by the formulas(R—Al—O)n and R(R—Al—O)nAlR2 where n is from 1 to about 20, and R ismost preferably methyl. The aluminoxanes are made by controlledhydrolysis of the corresponding aluminum trialkyl.

[0006] Another relatively early patent in the field, U.S. Pat. No.4,752,597 to Turner based on a filing date of 1985, describes olefinpolymerization catalysts comprising the reaction products of ametallocene complex of group IVB, VB, VIB, and VIII of the periodictable and an excess of aluminoxane. These catalysts are formed bypre-reacting a metallocene and an aluminoxane in mole ratios greaterthan 12:1, such as about 12:1 to about 100:1, to produce a solid productwhich precipitates from solution. Despite assertions of suitablecatalytic activity, in reality the activity of these materials is so lowas to be of no practical importance whatsoever.

[0007] In U.S. Pat. Nos. 4,960,878 and 5,041,584 to Crapo et al.modified methyl-aluminoxane is formed in several ways. One involvesreacting a tetraalkyldialuminoxane, R2Al—O—AlR2, containing C2 or higheralkyl groups with trimethylaluminum (TMA) at −10 to 150° C. Anotherinvolves reacting TMA with a polyalkylaluminoxane (—Al(R)—O—)n where Ris C2 alkyl or higher and n is greater than 1, e.g., up to 50.Temperatures suggested for this reaction are −20 to 50° C. A third wayinvolves conducting the latter reaction and then reacting the resultantproduct, which is indicated to be a complex between trimethylaluminumand the polyalkylaluminoxane, with water. The patent states that thewater-to-aluminum ratios used to make the polyalkylaluminoxane reagenthave an effect on the activity of the final methylaluminoxane. On thebasis of ethylene polymerizations using zirconocene dichloride catalystand a complex of trimethylaluminum with polyisobutylaluminoxanesubsequently reacted with water (MMAO) as co-catalyst, it is indicatedin the patent that the highest polymerization activities were achievedwith MMAO co-catalyst prepared at H2O/Al ratios of about 0.6 to about1.0 and Al/Zr ratios in the range of 10,000/1 to 400,000/1.

[0008] Various references are available indicating thatisobutylaluminoxanes themselves are relatively ineffective on their ownas co-catalysts. For example, several other reactions of alkylaluminumcompounds with water are disclosed in U.S. Pat. Nos. 4,960,878 and5,041,584. Thus in Example 1 of these patents, DIBAL-O(tetraisobutyldialuminoxane), a commercial product, was prepared byreaction of water with triisobutylaluminum (TIBA) in heptane using awater/TIBA ratio of about 0.5, followed by solvent stripping at 58-65°C. under vacuum. In Examples 3-6 of the patents isobutylaluminoxane(IBAO) was prepared by controlled addition of water to a 25% solution ofTIBA in toluene in the temperature range of 0-12° C., followed byheating to 70-80° C. to ensure complete reaction and remove dissolvedisobutane. H₂O/Al ratios used were 0.98, 1.21, 1.14, and 0.88. IBAO wasagain made in a similar manner in Example 52 of the patents. Here theH2O/Al ratio was 0.70, and the product was heated at 75° C. And inExample 70 tri-n-butylaluminum (TNBA) in toluene was treated at 0-10° C.with water followed by heating to 85° C. Ethylene polymerizations usingzirconocene dichloride catalyst and various products from the foregoingExamples were conducted. Specific activities (×103 gPE/(gZr.atmC2H4.hr)) of the catalysts made with DIBAL-O from Ex. 1, IBAO from Ex.3, and IBAO from Ex. 6 were, respectively, 4.1, 4.2, and 7.7, ascompared to 1000 for the catalyst made using conventional MAO as theco-catalyst. The patents acknowledge that tetraisobutyldialuminoxane(DIBAL-O) showed “poor polymerization activity”, and from the foregoingtest results the same can be said to apply to IBAO.

[0009] WO 96/02580 to Dall'occo, et al. describes olefin polymerizationcatalysts made by contacting a metallocene of Ti, Zr, or Hf, anorganoaluminum compound having at least one specified hydrocarbonsubstituent on the β-carbon atom of an aliphatic group bonded to analuminum atom, and water. Various ways of bringing these componentstogether are suggested. Polymerizations described were carried out usingAl/Zr mole ratios ranging from 500 up to as high as 5000.

[0010] EP 0277004 to Turner, published in 1988, describes the successfulpreparation and use as catalysts composed of an ionic pair derived fromcertain metallocenes of Group 4, most preferablybis(cyclopentadienyl)zirconium dimethyl or bis(cyclopentadienyl)hafniumdimethyl, reacted with certain trisubstituted ammonium salts of asubstituted or unsubstituted aromatic boron compound, most preferablyN,N-dimethylanilinium tetra(pentafluorophenyl)boron. While EP 0 277 004mentions that compounds containing an element of Groups V-B, VI-B,VII-B, VIII, I-B, II-B, III-A, IV-A, and V-A may be used in forming thecatalysts, no specific compounds other than boron compounds areidentified. In fact, EP 0 277 004 appears to acknowledge inability toidentify specific compounds other than boron compounds by stating:“Similar lists of suitable compounds containing other metals andmetalloids which are useful as second components could be made, but suchlists are not deemed necessary to a complete disclosure.” See in thisconnection Hlatky, Turner and Eckman, J. Am. Chem. Soc., 1989, 111,2728-2729, and Hlatky and Upton, Macromolecules, 1996, 29, 8019-8020.

[0011] U.S. Pat. No. 5,153,157 to Hlatky and Turner states that itsprocess “is practiced with that class of ionic catalysts referred to,disclosed, and described in European Patent Applications 277,003 and277, 004.” The process of U.S. Pat. No. 5,153,157 involves forming anionic catalyst system from two components. The first is abis(cyclopentadienyl) derivative of a Group IV-B metal compoundcontaining at least one ligand which will combine with the secondcomponent or portion thereof such as a cation portion thereof. Thesecond component is referred to as an ion exchange compound comprising(1) a cation which will irreversibly react with a ligand of the GroupIV-B metal compound and (2) a noncoordinating anion which is bulky,labile, and stable. The second component, also termed an activatorcomponent, comprises compounds of Groups V-B, VI-B, VII-B, VIII, I-B,II-B, III-A, IV-A, and V-A identified by a general formula. Besidesreferring to the boron compounds of EP 277,004, supra, such astri(n-butylammonium)tetra(pentafluorophenyl)boron andN,N-dimethylanilinium tetra(pentafluorophenyl)boron as suitableactivators, the U.S. '157 patent teaches use of boron compounds having aplurality of boron atoms, and also trialkyl aluminum compounds, triarylaluminum compounds, dialkylaluminum alkoxides, diarylaluminum alkoxides,and analogous compounds of boron. Of the organoaluminum activatorstriethylaluminum and trimethylaluminum are specified as most preferred.The Examples show use of a catalyst system formed from (1) a solution ofbis(cyclopentadienyl)zirconium dimethyl or bis(cyclopentadienyl)hafniumdimethyl and N,N-dimethylanilinium tetra(pentafluorophenyl)borontogether with (2) triethylborane, triethylaluminum, tri-sec-butylborane,trimethylaluminum, and diethylaluminum ethoxide. In some cases thecatalyst formed from the metallocene and the N,N-dimethylaniliniumtetra(pentafluorophenyl)boron without use of a compound of (2) gave nopolymer at all under the polymerization conditions used.

[0012] U.S. Pat. No. 5,198,401 to Turner, Hlatky, and Eckman refers, inpart, to forming catalyst compositions derived from certain metallocenesof Group 4, such as bis(cyclopentadienyl)zirconium dimethylorbis(cyclopentadienyl)hafnium dimethyl, reacted with certaintrisubstituted ammonium salts of a substituted or unsubstituted aromaticboron compound, such as N,N-dimethylaniliniumtetra(pentafluorophenyl)boron or tributylammoniumtetra(pentafluorophenyl)boron as in EP 0 277 004. However here the anionis described as being any stable and bulky anionic complex having thefollowing molecular attributes: 1) the anion should have a moleculardiameter about or greater than 4 angstroms; 2) the anion should formstable salts with reducible Lewis acids and protonated Lewis bases; 3)the negative charge on the anion should be delocalized over theframework of the anion or be localized within the core of the anion; 4)the anion should be a relatively poor nucleophile; and 5) the anionshould not be a powerful reducing or oxidizing agent. Anions of thistype are identified as polynuclear boranes, carboranes,metallacarboranes, polyoxoanions and anionic coordination complexes.Elsewhere in the patent it is indicated that any metal or metalloidcapable of forming a coordination complex which is resistant todegradation by water (or other Brønsted or Lewis acids) may be used orcontained in the second activator compound [the first activator compoundappears not to be disclosed]. Suitable metals of the second activatorcompound are stated to include, but not be limited to, aluminum, gold,platinum and the like. No such compound is identified. Again afterlisting boron compounds the statement is made that “Similar lists ofsuitable compounds containing other metals and metalloids which areuseful as second components could be made, but such lists are not deemednecessary to a complete disclosure.” In this connection, again noteHlatky, Turner and Eckman, J. Am. Chem. Soc., 1989, 111, 2728-2729, andHlatky and Upton, Macromolecules, 1996, 29, 8019-8020.

[0013] Despite the above and many other efforts involving aluminumco-catalysts, the fact remains that in order to achieve suitablecatalysis on a commercial basis, relatively high aluminum to transitionmetal ratios must be employed. Typically for optimal activity analuminum to metallocene ratio of greater than about 1000:1 is requiredfor effective homogeneous olefin polymerization. According toBrintzinger, et al., Angew. Chem. Int. Ed. Engl., 1995, 34 1143-1170:

[0014] “Catalytic activities are found to decline dramatically for MAOconcentrations below Al:Zr ratio roughly 200-300:1. Even at Al:Zr ratiosgreater than 1000:1 steady state activities increase with rising MAOconcentrations approximately as the cube root of the MAO concentration”.

[0015] This requirement of high aluminum loading is mainly caused by ametallocene activation mechanism in which generation of catalyticallyactive species is equilibriun driven. In this role MAO acts as a Lewisacid to remove by group transfer a leaving group X⊖ from the transitionmetal. This forms a weakly-coordinating anion, MAO-X⊖, in thecorresponding transition metal cation. That is, in such systems thefollowing equilibrium exists:

[0016] The Lewis acid sites in MAO abstract a negatively charged leavinggroup such as a methide group from the metallocene to form thecatalytically active ion pair. The activation process is reversible andKeq is typically small. Thus the ion pair can return to its neutralprecursors which are catalytically inactive. To overcome this effect, alarge excess of MAO is required to drive the equilibrium to the right.

[0017] The high aluminum loadings required for effective catalysis insuch systems result in the presence of significant levels ofaluminum-containing residues (“ash”) in the polymer. This can impair theclarity of finished polymers formed from such catalyst systems.

[0018] A farther disadvantage of MAO is its limited solubility inparaffinic hydrocarbon solvents. Polymer manufacturers would find it ofconsiderable advantage to have in hand aluminoxane and metallocene-basedmaterials having high paraffin solubility.

[0019] Still another disadvantage of MAO has been its relatively highcost. For example, in an article entitled “Economics is Key to Adoptionof Metallocene Catalysts” in the Sep. 11, 1995 issue of Chemical &Engineering News, Brockmeier of Argonne National Laboratory concludedthat “a reduction in costs or amount of MAO has the potential forgreatly reducing the costs to employ metallocene catalysts”.

[0020] Thus it would be of inestimable value to the art if a way couldbe found of providing catalyst components based on use of aluminoxanesthat are effective co-catalysts for use with transition metal compoundsat much lower aluminum:metal ratios than have been effective heretofore.In addition, the art would be greatly advanced if this could beaccomplished with aluminoxane compositions that are less expensive thanMAO, that have high solubility in paraffinic solvents and that producelower ash residues in the polymers.

[0021] The invention described and claimed in U.S. Pat. No. 6,160,145 isdeemed to have fulfilled most, if not all, of the foregoing desirableobjectives. In brief summary, that invention makes it possible toprovide catalyst compositions in which a low cost co-catalyst can beemployed at very low Al loadings. Such catalyst compositions typicallyhave high solubility in paraffinic solvents. Moreover they yield reducedlevels of ash and result in improved clarity in polymers formed fromsuch catalyst compositions. Making all of this possible is the provisionof a compound which comprises (i) a cation derived from a transition,lanthanide or actinide metal compound, preferably a metallocene, by lossof a leaving group, and (ii) an aluminoxate anion (a.k.a. aluminoxanateanion) derived by transfer of a proton from a stable or metastablehydroxyaluminoxane to said leaving group. In contrast to aluminoxanesused prior to the Parent Application and acting as Lewis acids (Eq. 1),the present compositions utilize hydroxyaluminoxane species (HO—AO)acting as Brønsted acids. In the formation of such compounds, a cationis derived from the transition, lanthanide or actinide metal compound byloss of a leaving group, and this cation forms an ion pair with analuminoxate anion devoid of such leaving group. The leaving group istypically transformed into a neutral hydrocarbon thus rendering thecatalyst-forming reaction irreversible as shown in Equation 2:

Cp2MXR+HO—AO[Cp2M—X]⊖(O—AO)⊖+RH  (Eq. 2)

[0022] Note the absence of the leaving group, X, in the anion OAO⊖ ascompared to the presence of X in the anion, (X-MAO)⊖, of Equation 1.

[0023] In many of the patents related to the use of aluminoxanes asmetallocene co-catalysts, rather broad and generalized assertions havebeen routinely made regarding aluminum-to-metallocene ratio, types ofalkyl aluminoxanes, and ratio of water to aluminum for formingaluminoxanes. However, there is no disclosure of any type that wouldsuggest, let alone demonstrate, the use of an aluminoxane as a Brønstedacid to activate metallocenes and related organometallic catalysts.There are, furthermore, no known prior teachings or descriptions of howto use an aluminoxane as a Brønsted acid muchless that by so doing itwould be possible to reduce the ratio of aluminum to transition,lanthanide or actinide metal to an unprecedentedly low level.

[0024] In another of its embodiments the invention of U.S. Pat. No.6,160,145 provides a process which comprises contacting a transition,lanthanide or actinide metal compound having at least two leaving groupswith a hydroxyaluminoxane in which at least one aluminum atom has ahydroxyl group bonded thereto so that one of said leaving groups islost. As noted above, during the formation of such compounds, analuminoxate anion is formed that is devoid of the leaving group. Insteadthe leaving group is typically transformed into a neutral hydrocarbon sothat the catalyst forming reaction is irreversible.

[0025] Still another embodiment of the invention of U.S. Pat. No.6,160,145 is a process of polymerizing at least one polymerizableunsaturated monomer, which process comprises contacting said monomerunder polymerization conditions with a compound which comprises a cationderived from a transition, lanthanide or actinide metal compound,preferably a metallocene, by loss of a leaving group and an aluminoxateanion derived by transfer of a proton from a stable or metastablehydroxyaluminoxane to said leaving group.

[0026] Other embodiments of the invention of U.S. Pat. No. 6,160,145include catalyst compositions in which a compound comprising a cationderived from a transition, lanthanide or actinide metal compound,preferably a metallocene, by loss of a leaving group and an aluminoxateanion derived by transfer of a proton from a stable or metastablehydroxyaluminoxane to said leaving group is supported on a carrier.

[0027] As described in U.S. patent application Ser. No. 09/655,218,filed Sep. 5, 2000 (hereinafter the “'218 Application”), the catalystcompositions described in U.S. Pat. No. 6,160,145 and also herein canhave exceptional stability once recovered and maintained under suitableconditions in the absence of a solvent. The '218 Application describesstorage of a solid catalyst of this type in a drybox at ambient roomtemperatures for a one-month period without loss of its catalyticactivity. In contrast, the same catalyst composition is relativelyunstable if left in the reaction solution or put in solution after ithas been removed from solution. The added features of this invention areto recover the catalyst composition (catalytic compound) after itspreparation, optionally subject the catalyst composition to one or morefinishing procedures and/or optionally mix the catalyst composition withone or more inert substances under suitable inert anhydrous conditions,and store the catalyst composition by itself, in supported form or as asolvent-free mixture with one or more inert substances under suitableconditions which minimize exposure to moisture and air (oxygen) as muchas reasonably possible.

[0028] Thus in one of the embodiments described in the '218 Applicationis a compound which comprises a cation derived from d-block or f-blockmetal compound by loss of a leaving group and an aluminoxate anionderived by transfer of a proton from a stable or metastablehydroxyaluminoxane to said leaving group, wherein such compound is inundissolved form in a dry, inert atmosphere or environment. Preferablythe compound in such atmosphere or environment is in isolated form or isin supported form on a catalyst support.

[0029] Another embodiment described in the '218 Application is acompound which comprises a cation derived from a d-block or f-blockmetal compound by loss of a leaving group and an aluminoxate aniondevoid of said leaving group, wherein the compound comprised of suchcation and aluminoxate anion is in undissolved form in a dry, inertatmosphere or environment. Preferably the compound in such atmosphere orenvironment is in isolated form or is in supported form on a catalystsupport.

[0030] A further embodiment described in the '218 Application is acompound which comprises a cation derived from a d-block or f-blockmetal compound by loss of a leaving group transformed into a neutralhydrocarbon, and an aluminoxate anion derived by loss of a proton from ahydroxyaluminoxane having, prior to said loss, at least one aluminumatom having a hydroxyl group bonded thereto, wherein the compoundcomprised of such cation and aluminoxate anion is in undissolved formexcept during one or more optional finishing procedures, if and when anysuch finishing procedure is performed. In addition, the compound is keptin a dry, inert atmosphere during a storage period. Preferably thecompound in such atmosphere or environment is in isolated form or is insupported form on a catalyst support.

[0031] The compounds of each of the above embodiments of the '218Application can be used as a catalyst either in the solid state or insolution. The stability of the compound when in solution is sufficientto enable the compound to perform as a homogeneous catalyst.

[0032] Still another embodiment described in the '218 Application is aprocess which comprises contacting a d-block or f-block metal compoundhaving at least two leaving groups with a hydroxyaluminoxane in which atleast one aluminum atom has a hydroxyl group bonded thereto so that oneof said leaving groups is lost; recovering the resultantmetal-containing compound so formed; and storing such recovered compound(preferably in isolated form or in supported form on a catalyst support)in an anhydrous, inert atmosphere or environment. Such compound ismaintained in undissolved form except during one or more optionalfinishing procedures, if and when any such finishing procedure isperformed.

[0033] Also provided as another embodiment of the '218 Application is aprocess which comprises donating a proton from an aluminoxane to aleaving group of a d-block or f-block metal compound to form a compoundcomposed of a cation derived from said metal compound and an aluminoxateanion devoid of said leaving group; recovering the compound composed ofsuch cation and aluminoxate anion; storing such recovered compound(preferably in isolated form or in supported form on a catalyst support)in an anhydrous, inert atmosphere or environment; and maintaining suchcompound in undissolved form except during one or more optionalfinishing procedures, if and when any such finishing procedure isperformed.

[0034] Another embodiment of the '218 Application is a process whichcomprises interacting a d-block or f-block metal compound having twoleaving groups and a hydroxyaluminoxane having at least one aluminumatom that has a hydroxyl group bonded thereto to form a compoundcomposed of a cation through loss of a leaving group which istransformed into a neutral hydrocarbon, and an aluminoxate anion derivedby loss of a proton from said hydroxyaluminoxane; recovering thecompound composed of such cation and aluminoxate anion; storing suchrecovered compound (preferably in isolated form or in supported form ona catalyst support) in an anhydrous, inert atmosphere or environment;and maintaining such compound in undissolved form except during one ormore optional finishing procedures, if and when any such finishingprocedure is performed.

[0035] Still other embodiments are described in the '218 Application.

[0036] Notwithstanding all of the foregoing advances, the meta-stablenature of the hydroxy groups in the hydroxyaluminoxane species ofaluminoxanes can have an negative impact upon the shelf life of thisspecies of compounds. Increasing the steric bulk of these compounds doesappear to increase the lifetime of their OH groups (see, e.g., FIG. 6),but not sufficiently to meet the anticipated needs of commercialapplications. Storage of these compounds at low temperature, e.g., circa−10° C., can significantly increase the compound lifetime (see, e.g.,FIG. 7), but cost and operational considerations of this technique alsoare less that ideal for commercial applications.

[0037] Accordingly, a need exists for a way to significantly increasingthe lifetime of the OH groups in hydroxyaluminoxanes, preferably at ornear room temperature. A need also exists for a facile way to employolefin polymerization catalysts while avoiding reactor fouling.

BRIEF SUMMARY OF THE INVENTION

[0038] The present invention is deemed to meet these and other needs ina surprisingly novel way. It has now been found that hydroxyaluminoxanescan be converted into novel, solid compositions of matter, so as todrastically increase the lifetime of the hydroxy group(s) in thecomposition (i.e., reduce the composition OH-decay rate), even at roomtemperature, while at the same time reducing, if not eliminating,reactor fouling.

[0039] Thus, one embodiment of this invention provides a composition inthe form of one or more individual solids, which composition is formedfrom components comprised of (i) a hydroxyaluminoxane and (ii) a carriermaterial compatible with said hydroxyaluminoxane and in the form of oneor more individual solids, said composition having a reduced OH-decayrate relative to the OH-decay rate of (i).

[0040] This invention also provides in another embodiment a compositionwhich comprises a hydroxyaluminoxane supported on a solid support.

[0041] Yet another embodiment of the present invention is a processcomprising converting a hydroxyaluminoxane into a composition in theform of one or more individual solids by bringing together (i) ahydroxyaluminoxane and (ii) a carrier material compatible with saidhydroxyaluminoxane and in the form of one or more individual solids,whereby the rate of OH-decay for said composition is reduced relative tothe rate of OH-decay of (i).

[0042] Still another embodiment of the present invention is a supportedactivated catalyst composition formed by bringing together (A) acomposition in the form of one or more individual solids, whichcomposition is formed from components comprised of (i) ahydroxyaluminoxane and (ii) a carrier material compatible with saidhydroxyaluminoxane and in the form of one or more individual solids,said composition of (A) having a reduced OH-decay rate relative to theOH-decay rate of (i); and (B) a d- or f-block metal compound having atleast one leaving group on a metal atom thereof.

[0043] This invention also provides a process of preparing a supportedactivated catalyst, which process comprises bringing together (A) acomposition in the form of one or more individual solids formed bybringing together (i) a hydroxyaluminoxane and (ii) a carrier materialcompatible with said hydroxyaluminoxane and in the form of one or moreindividual solids, whereby the rate of OH-decay for said composition isreduced relative to the rate of OH-decay of (i); and (B) a d- or f-blockmetal compound having at least one leaving group on a metal atomthereof.

[0044] In another embodiment of this invention, an olefin polymerizationprocess is provided which comprises bringing together in apolymerization reactor or reaction zone (1) at least one polymerizableolefin and (2) a supported activated catalyst composition which is inaccordance with this invention.

[0045] Still another embodiment of this invention is a catalystcomposition formed by bringing together (A) a hydroxyaluminoxane and (B)rac-ethylenebis(1-indenyl)zirconium dimethyl.

[0046] A further embodiment of the invention provides a process for theproduction of a supported hydroxyaluminoxane which comprises bringingtogether (i) an aluminum alkyl in an inert solvent, (ii) a water source,and (iii) a carrier material, under hydroxyaluminoxane-forming reactionconditions.

[0047] Still another embodiment is a method of forming an olefinpolymerization catalyst, which method comprises introducing into areactor or a reaction zone (A) a hydroxyaluminoxane and (B) a d- orf-block metal compound in proportions such that an active olefinpolymerization catalyst is formed. In this embodiment, thehydroxyaluminoxane preferably is fed in the form of (i) a solution ofthe hydroxyaluminoxane in an inert solvent or in a liquid polymerizableolefinic monomer, or both; (ii) a slurry of the hydroxyaluminoxane in aninert diluent or in a liquid polymerizable olefinic monomer; (iii)unsupported solid particles; or (iv) one or more solids on a carriermaterial or catalyst support; or (v) any combination of two or more of(i), (ii), (iii), and (iv). More preferably, the hydroxyaluminoxane willbe fed in the form of one or more solids on a carrier material suspendedin an inert viscous liquid, e.g., mineral oil. Similarly, the d- orf-block metal compound preferably is fed in the form of (i) undilutedsolids or liquid, or (ii) a solution or slurry of the d- or f-blockmetal compound in an inert solvent or diluent, or in a liquidpolymerizable olefinic monomer, or in a mixture of any of these. Morepreferably, the d- or f-block metal compound will be fed in the form ofa solution or slurry of the metal compound in an inert solvent ordiluent. It is also preferred that the catalyst be formed from onlycomponents (A) and (B). The introduction of (A) and (B) into the reactoror reaction zone can proceed in any given order or sequence, or canproceed concurrently. Also, the introduction of (A) and (B) into thereactor or reaction zone can proceed continuously or intermittently.Preferably, the metal compound is fed into the hydroxyaluminoxane, andmore preferably the metal compound in the form of a solution or slurryin an inert solvent or diluent will be fed to the hydroxyaluminoxane inthe form of one or more solids on a carrier material suspended in aninert viscous liquid.

[0048] As another of its embodiments, this invention also provides, in aprocess for the catalytic polymerization of at least one olefin in apolymerization reaction vessel or reaction zone, the improvement whichcomprises introducing into the reaction vessel or reaction zone catalystcomponents comprising (A) a hydroxyaluminoxane and (B) a d- or f-blockmetal compound, in proportions such that said at least one olefin ispolymerized. Components (A) and (B) can be introduced into thepolymerization reactor vessel or zone as separate feeds, eithercontinuously or intermittently, and either concurrently or in anysequence. Alternatively, they can be brought together and allowed tointeract with each other for a suitable period of time with theresultant composition then being introduced into the polymerizationreactor or zone. Other polymerization components, e.g., aluminum alkyl,ordinary hydroxyaluminoxane, etc., can be introduced before, during, orafter the introduction of (A) and (B) or either of them or of apreformed catalyst formed by interaction between (A) and (B). The formsin which the hydroxyaluminoxane and the d- or f-block metal compound arefed into the polymerization reactor or zone can be any of thosedescribed in the immediately preceding paragraph.

[0049] The above and other embodiments, features, and advantages of thisinvention will become still further apparent from the ensuingdescription and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0050]FIG. 1 is an infrared spectrum of hydroxyisobutylaluminoxane(HO-IBAO) useful in the practice of this invention.

[0051]FIG. 2 is a superimposed series of infrared spectra of HO-IBAOillustrating the loss of hydroxyl groups at intervals during a two-dayperiod at ambient temperature.

[0052]FIG. 3 is a superimposed series of infrared spectra, the topspectrum being that of a fresh HO-IBAO, the middle spectrum being thatof the same HO-IBAO but taken 30 minutes later, and the bottom spectrumbeing that a catalyst composition of this invention formed from thereaction between rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl(MET-A) and HO-IBAO showing that the activation of a metallocene havinga suitable leaving group is accompanied by a rapid loss of hydroxylgroups, consistent with HO-IBAO functioning as a Brønsted acid inmetallocene activation.

[0053]FIG. 4 are superimposed UV-Vis spectra, the top spectrum beingthat of MET-A, the middle spectrum being that of a catalyst compositionof this invention having an Al/Zr ratio of 21/1 formed from the reactionbetween MET-A and HO-IBAO, and the bottom spectrum being that of acatalyst composition of this invention having an Al/Zr ratio of 11/1formed from the reaction between MET-A and HO-IBAO.

[0054]FIG. 5 are superimposed UV-Vis spectra, the top spectrum beingthat of MET-A, the middle spectrum being that of a composition formedfrom MET-A and isobutylaluminoxane (IBAO) that resulted from loss ordepletion of hydroxyl groups from IBAO, and the bottom spectrum beingthat of tetraisobutyldialuminoxane (TIBAO).

[0055]FIG. 6 is a graph illustrating the change in infrared—OHabsorption over time at room temperature for HO-IBAO and forhydroxyisooctylaluminoxane (HO-IOAO).

[0056]FIG. 7 is a graph illustrating the change in infrared—OHabsorption over time at −10° C. for HO-IBAO and for HO-IOAO.

[0057]FIG. 8 is a DRIFTS subtraction spectrum of DO-IBAO/silica andHO-IBAO/silica.

[0058]FIG. 9 is a H¹-nmr spectrum of the distillate fromBnMgCl+DO-IBAO/silica.

[0059]FIG. 10 is a graph illustrating the change in the number of OHgroups per 100 Aluminum atoms over time at room temperature for HO-IBAOat −10° C., HO-IBAO/silica(1) and HO-IBAO/silica(2).

FURTHER DETAILED DESCRIPTION OF THE INVENTION

[0060] Hydroxyaluminoxane Reactants

[0061] Unlike catalyst compositions formed from a transition, lanthanideor actinide metal compound (hereinafter “d- or f-block metal compound”)and MAO or other previously recognized aluminoxane co-catalyst species,the catalyst compositions of U.S. Pat. No. 6,160,145 and U.S. patentapplication Ser. No. 09/655,218 are formed from a hydroxyaluminoxane.The hydroxyaluminoxane has a hydroxyl group bonded to at least one ofits aluminum atoms. To form these hydroxyaluminoxanes, a sufficientamount of water is reacted with an alkyl aluminum compound to result information of a compound having at least one HO—Al group and havingsufficient stability to allow reaction with a d- or f-blockorganometallic compound to form a hydrocarbon.

[0062] The alkyl aluminum compound used in forming thehydroxyaluminoxane reactant can be any suitable alkyl aluminum compoundother than trimethylaluminum. Thus at least one alkyl group has two ormore carbon atoms. Preferably each alkyl group in the alkyl aluminumcompound has at least two carbon atoms. More preferably each alkyl grouphas in the range of 2 to about 24, and still more preferably in therange of 2 to about 16 carbon atoms. Particularly preferred are alkylgroups that have in the range of 2 to about 9 carbon atoms each. Thealkyl groups can be cyclic (e.g., cycloalkyl, alkyl-substitutedcycloalkyl, or cycloalkyl-substituted alkyl groups) or acyclic, linearor branched chain alkyl groups. Preferably the alkyl aluminum compoundcontains at least one, desirably at least two, and most preferably threebranched chained alkyl groups in the molecule. Most preferably eachalkyl group of the aluminum alkyl is a primary alkyl group, i.e., thealpha-carbon atom of each alkyl group carries two hydrogen atoms.

[0063] Suitable aluminum alkyl compounds which may be used to form thehydroxyaluminoxane reactant include dialkylaluminum hydrides andaluminum trialkyls. Examples of the dialkylaluminum hydrides includediethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminumhydride, di(2,4,4-trimethylpentyl)aluminum hydride,di(2-ethylhexyl)aluminum hydride, di(2-butyloctyl)aluminum hydride,di(2,4,4,6,6-pentamethylheptyl)aluminum hydride,di(2-hexyldecyl)aluminum hydride, dicyclopropylcarbinylaluminum hydride,dicyclohexylaluminum hydride, dicyclopentylcarbinylaluminum hydride, andanalogous dialkylaluminum hydrides. Examples of trialkylaluminumcompounds which may be used to form the hydroxyaluminoxane includetriethylaluminum, tripropylaluminum, tributylaluminum,tripentylaluminum, trihexylaluminum, triheptylaluminum,trioctylaluminum, and their higher straight chain homologs;triisobutylaluminum, tris(2,4,4-trimethylpentyl)aluminum,tri-2-ethylhexylaluminum, tris(2,4,4,6,6-pentamethylheptyl)aluminum,tris(2-butyloctyl)aluminum, tris(2-hexyldecyl)aluminum,tris(2-heptylundecyl)aluminum, and their higher branched chain homologs;tri(cyclohexylcarbinyl)aluminum, tri(2-cyclohexylethyl)aluminum andanalogous cycloaliphatic aluminum trialkyls. Triisobutylaluminum hasproven to be an especially desirable alkyl aluminum compound forproducing a hydroxyaluminoxane.

[0064] To prepare the hydroxyaluminoxane a solution of the alkylaluminum compound in an inert solvent, preferably a saturated oraromatic hydrocarbon, is treated with controlled amounts of water whilemaintaining the vigorously agitated reaction mixture at low temperature,e.g., below about 0° C. When the exothermic reaction subsides, thereaction mixture is stored at a low temperature, e.g., below about 0° C.until used in forming a compound of this invention. When preparing ahydroxyaluminoxane from a low molecular weight alkylaluminum compound,the reaction mixture can be subjected, if desired, to stripping undervacuum at a temperature below room temperature to remove some loweralkane hydrocarbon co-product formed during the reaction. However, suchpurification is usually unnecessary as the lower alkane co-product ismerely an innocuous impurity.

[0065] Among suitable procedures for preparing hydroxyaluminoxanes foruse in practice of this invention, is the method described by Ikonitskiiet al., Zhurnal Prikladnoi Khimii, 1989, 62(2), 394-397; and the Englishlanguage translation thereof available from Plenum PublishingCorporation, copyright 1989, as Document No. 0021-888X/89/6202-0354.

[0066] It is very important to slow down the premature loss of itshydroxyl group content sufficiently to maintain a suitable level of OHgroups until the activation reaction has been effected. One way toaccomplish this is to maintain the temperature of the hydroxyaluminoxaneproduct solution sufficiently low. This is demonstrated by the datapresented graphically in FIG. 2 which shows the loss of hydroxyl groupsfrom hydroxyisobutylaluminoxane at ambient room temperature in an IRcell. If, on the other hand, the same hydroxyaluminoxane solution isstored in a freezer at −10° C., the rate of hydroxyl group loss isreduced to such a degree that the time scale for preserving the sameamount of hydroxyl groups can be lengthened from one to two hours atambient room temperature to one to two weeks at −10° C. If the hydroxylgroup content is lost, the compound reverts to an aluminoxane which isincapable of forming the novel ionic highly active catalytic compoundsof this invention.

[0067] It is also important when preparing the hydroxyaluminoxanes touse enough water to produce the hydroxyaluminoxane, yet not so muchwater as will cause its destruction. Typically the water/aluminum moleratio is in the range of about 0.5/1 to about 1.2/1, and preferably inthe range of 0.8/1 to 1.1/1. At least in the case ofhydroxyisobutylaluminoxane, these ratios typically result in theformation of hydroxyaluminoxane having at least about one hydroxyl groupfor every seven aluminum atoms in the overall product. Thehydroxyisobutylaluminoxane is essentially devoid of unreactedtriisobutylaluminum.

[0068] However, it now has been discovered that the rate of OH-decay(i.e., the rate at which OH groups disassociate so as to reduce thenumber of OH groups present in the molecule) for the above-describedhydroxyalumioxane may be drastically and surprisingly reduced byconverting hydroxyaluminoxane into a composition in the form of one ormore individual solids having an OH-decay rate which is reduced relativeto the OH-decay rate of the hydroxyaluminoxane. Such a composition isformed by bringing together the hydroxyaluminoxane and a carriermaterial which is compatible with the hydroxyaluminoxane and which is inthe form of one or more individual solids. In bringing these twocomponents together, it is preferred that the hydroxyaluminoxane becomessupported upon the carrier material. Typically, the rate of OH-decay forthe composition so formed is reduced by a factor of at least 5, and morepreferably at least 10, as compared to the rate of OH-decay of thehydroxyaluminoxane. The composition formed from the hydroxyaluminoxaneand carrier material itself may be used to form active polymerizationcatalysts of this invention. Such compositions remain active as aBrønsted acid for a surprisingly greater period of time as compared tothat of the hydroxyaluminoxane.

[0069] When it is stated herein that the composition so formed or thecarrier material is “in the form of one or more individual solids,” itis meant that the composition or carrier material, as the case may be,is solid matter, regardless of whether it takes the form of a singlesolid slab or unitary piece of matter in solid form, or the form of amass made up of a plurality of unitary pieces of matter in solid form,e.g., particles, pellets, micropellets, beads, crystals, agglomerates,etc. or the form of some other macromolecular structure. Preferably, thecarrier material is in particulate form, and more preferably is inparticulate form having a surface area of typically at least about 20,preferably at least about 30, and most preferably from at least about 50m²/g, which surface area can range typically from about 20 to about 800,preferably from about 30 to about 700, and most preferably from about 50to about 600 m²/g. It is also preferred that the carrier materialparticulate have a bulk density of typically at least about 0.15,preferably at least about 0.20, and most preferably at least about 0.25g/ml, which bulk density can range typically from about 0.15 to about 1,preferably from about 0.20 to about 0.75, and most preferably from about0.25 to about 0.45 g/ml. Preferably, the carrier particulate has anaverage pore diameter of typically from about 30 to about 300, and mostpreferably from about 60 to about 150 Angstroms. The carrier particulatealso preferably has a total pore volume of typically about 0.10 to about2.0, more preferably from about 0.5 to about 1.8, and most preferablyfrom about 0.8 to about 1.6 cc/g. The average particle size and itsdistribution will be dictated and controlled by the type ofpolymerization reaction contemplated for the catalyst composition. As ageneralization, the average particle size will be in the range of fromabout 4 to about 250, and preferably in the range of about 8 to about100 microns. However, with respect to specific processes, solutionpolymerization processes, for example, typically can employ an averageparticle size in the range of about 1 to about 10 microns, while acontinuous stirred tank reactor slurry polymerization typically canemploy an average particle size in the range of about 8 to about 50microns, a loop slurry polymerization typically can employ an averageparticle size in the range of about 10 to about 150 microns, and a gasphase polymerization typically can employ an average particle size inthe range of about 20 to about 120 microns. Other sizes may also bepreferred under varying circumstances. When the carrier material isformed by spray drying, it is also preferable that typically at least80, more preferably at least 90, and most preferably at least 95 vol.percent of that fraction of the carrier particles smaller than the Dgoof the entire carrier particulate particle size distribution possessesmicrospheroidal shape (i.e., morphology). Also, when it is said that thecarrier material is “compatible” with the hydroxyaluminoxane, it ismeant that the carrier material is capable of coming into proximity orcontact with, or being mixed with or otherwise placed in the presenceof, the hydroxyaluminoxane without adversely affecting the ability ofthe hydroxyaluminoxane to activate the metal compound elsewheredescribed herein to form the polymerization catalysts of this invention.

[0070] The carrier material used in the practice of this invention ispreferably a solid support. Non-limiting examples of such solid supportswill include particulate inorganic catalyst supports such as, e.g.,inorganic oxides (e.g., silica, silicates, silica-alumina, alumina)clay, clay minerals, ion exchanging layered compounds, diatomaceousearth, zeolites, magnesium chloride, talc, and the like, includingcombinations of any two or more of the same, and particulate organiccatalyst supports such as, e.g., particulate polyethylene, particulatepolypropylene, other polyolefin homopolymers or copolymers, and thelike, including combinations of any two or more of the same. Particulateinorganic catalyst supports are preferred. It is also preferred that thesupport be anhydrous or substantially anhydrous. More preferred isparticulate calcined silica, which is optionally pretreated inconventional manner with a suitable aluminum alkyl, e.g., triethylaluminum. In certain applications, it may be preferred to suspend thecarrier material in a viscous inert liquid, e.g., mineral oil. Theviscosity of such inert liquid can vary depending upon the carriermaterial involved, but such viscous inert material is most preferablyviscous enough to retain the carrier material (and any materialsupported thereupon) in suspension over a desired period of time or atleast to permit of resuspension of the support (and any materialsupported thereupon) with agitation (e.g., stirring) after settling.Exemplary viscous inert liquid will preferably have a viscosity in therange of about 1 to about 2000 centipoise, and more preferably in therange of about 200 to about 1500 centipoise, at ambient temperature.

[0071] The amount of hydroxyaluminoxane in the composition whichincludes a carrier material typically will be about 5 to about 50 weightpercent, preferably about 10 to about 40 weight percent, and morepreferably about 20 to about 30 weight percent, hydroxyaluminoxane basedupon the total weight of the composition, with the balance being made upof the carrier material.

[0072] The reaction conditions under which the carrier material and thehydroxyaluminoxane may be brought together may vary widely, buttypically will be characterized with a temperature in the range of about−20 to about 100° C., using superatmospheric, subatmospheric oratmospheric pressure (so long as the desired product is formed) and aninert atmosphere or environment. These components may be broughttogether in any of a variety ofways, including, e.g., by feeding thehydroxyaluminoxane and the carrier material concurrently or sequentiallyin any sequence, and mixing the components together, preferably in aninert liquid medium, or by otherwise mixing or contacting thesecomponents with each other, again preferably in an inert liquid medium.The liquid medium can be separately fed to the mixing vessel before,during, and/or after feeding or otherwise introducing thehydroxyaluminoxane and/or the carrier material. Similarly, thehydroxyaluminoxane can be fed as a solution or slurry in the liquidmedium, and/or, the carrier material when in particulate form can be fedas a slurry in the liquid medium to thereby provide all or a part of thetotal liquid medium being used. Such procedures can be conducted eitherin batch, continuously or intermittently. Preferably, the carriermaterial and the hydroxyaluminoxane will be brought together in thepresence of an inert solvent in which the hydroxyaluminoxane isdissolved, e.g., in an inert organic solvent such as a saturatedaliphatic or cycloaliphatic hydrocarbon, or an aromatic hydrocarbon, ora mixture of any two or more such hydrocarbons.

[0073] For quantitative purposes with respect to the number of hydroxylgroups present in the hydroxyaluminoxane or in the composition madetherefrom, a deuterium-labeled DO-hydroxyaluminoxane/carrier preferablyis used when the carrier material includes hydroxyl groups (e.g.,silica). Typically, samples will be stored at room temperature in adrybox and sampled periodically for quantitative analysis to determinethe rate of OH-decay at given points in time. A typical procedure withrespect to deuterium-labeled hydroxyisobutylaluminoxane/silica isdescribed below in Example 28. This procedure will preferably beemployed to quantify the hydroxyl groups (as DO-per 100 aluminum atoms)present in the composition at or near the time of fresh preparation(i.e., time zero), and at one or more intervals of time thereafter,preferably at 48 hours or more preferably at 72 hours followingpreparation of the sample materials. The change in the number ofhydroxyl groups at the selected time interval from that at time zero,divided by the amount of time, will be the OH-decay rate. When thecarrier material does not include hydroxyl groups, or when the samplematerial is unsupported hydroxyaluminoxane, this same procedure may beemployed but without deuterium labeling.

[0074] These co-catalyst compositions formed from the hydroxyaluminoxaneand the carrier material may be formed and isolated prior to use as acatalyst component, or they may be formed in situ, such as, e.g., duringthe process of production of the hydroxyaluminoxane itself. Accordingly,these compositions may be formed by addition of the carrier materialduring the synthesis of hydroxyaluminoxane. Thus, for example, thecarrier material may be introduced at any point during the synthesisprocesses described hereinabove for the hydroxyaluminoxane, so as tobring an aluminum alkyl in solution together with a water source and thecarrier material under hydroxyaluminoxane-forming reaction conditions.Besides free water, other non-limiting examples of a suitable watersource include hydrates of alkali or alkaline earth metal hydroxidessuch as, for example, lithium, sodium, potassium, barium, calcium,magnesium, and cesium hydroxides (e.g., sodium hydroxide mono- anddihydrate, barium hydroxide octahydrate, potassium hydroxide dihydrate,cesium hydroxide monohydrate, lithium hydroxide monohydrate, and thelike), aluminum sulfate, certain hydrated catalyst support materials(e.g., un-dehydrated silica), as well as mixtures of any two or more ofthe foregoing. The reaction conditions for this in situ formation willtypically be the same as those reactions conditions taught herein forforming the hydroxyaluminoxane generally.

[0075] When forming co-catalyst compositions from the hydroxyaluminoxaneand the carrier material, it is preferred that the hydroxyaluminoxanehave less than 25 OH groups per 100 aluminum atoms, and even morepreferred that they have no more than 15 OH groups per 100 aluminumatoms. In certain other embodiments of this invention, it is alsopreferred that the composition so made be substantially insoluble in aninert organic solvent such as various hydrocarbons, e.g., saturatedaliphatic or cycloaliphatic hydrocarbons.

[0076] These compositions formed from a hydroxyaluminoxane may beemployed as the olefin polymerization co-catalyst in place of the lessstable hydroxyaluminoxane, to provide a surprisingly more stable yetequally effective co-catalyst and catalyst composition in commercialapplications.

[0077] d- or f-Block Metal Compound

[0078] Various d- and f-block metal compounds may be used in forming thecatalytically active compounds of this invention. The d-block andf-block metals of this reactant are the transition, lanthanide andactinide metals. See, for example, the Periodic Table appearing on page225 of Moeller, et al., Chemistry, Second Edition, Academic Press,Copyright 1984. As regards the metal constituent, preferred arecompounds of Fe, Co, Pd, and V. More preferred are compounds of themetals of Groups 4-6 (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W), and mostpreferred are the Group 4 metals, especially hafnium, and mostespecially zirconium.

[0079] A vital feature of the d- or f-block metal compound used informing the ionic compounds of this invention is that it must contain atleast one leaving group that forms a separate co-product by interactionwith a proton from the hydroxyaluminoxane or that interacts with aproton from the hydroxyaluminoxane so as to be converted from a cyclicdivalent group into an open chain univalent group bonded to the metalatom of the metallocene. Thus the activity of the chemical bond betweenthe d- or f-block metal atom and the leaving group must be at leastcomparable to and preferably greater than the activity of thealuminum-carbon bond of the hydroxyaluminoxane. In addition, thebasicity of the leaving group must be such that the acidity of itsconjugate acid is comparable to or less than the acidity of thehydroxyaluminoxane. Univalent leaving groups that meet these criteriainclude hydride, hydrocarbyl and silanylcarbinyl (R₃SiCH₂—) groups, suchas methyl, ethyl, vinyl, allyl, cyclohexyl, phenyl, benzyl,trimethylsilanylcarbinyl, amido, alkylamido, substituted alkylamido,etc. Of these, the methyl group is the most preferred leaving group.Suitable divalent cyclic groups that can serve as leaving groups by aring opening mechanism whereby a cyclic group is converted into an openchain group that is still bonded to the metal atom of the metalloceneinclude conjugated diene divalent anionic ligand groups such as aconjugated diene or a hydrocarbyl-, halocarbyl-, or silyl substitutedderivative thereof, such conjugated diene anionic ligand groups havingfrom 4 to about 40 nonhydrogen atoms and being coordinated to the metalatom of the metallocene so as to form a metallocyclopentene therewith.Typical conjugated diene ligands of this type are set forth for examplein U.S. Pat. No. 5,539,068.

[0080] Metallocenes make up a preferred class of d- and f-block metalcompounds used in making the ionic compounds of this invention. Thesecompounds are characterized by containing at least one cyclopentadienylmoiety pi-bonded to the metal atom. For use in this invention, themetallocene must also have bonded to the d- or f-block metal atom atleast one leaving group capable of forming a stable co-product oninteraction with a proton from the hydroxyaluminoxane. A halogen atom(e.g., a chlorine atom) bonded to such metal atom is incapable ofserving as a leaving group in this regard in as much as the basicitiesof such halogen atoms are too low.

[0081] Such leaving groups may be prepared separately or in situ. Forexample, metallocene halides may be treated with alkylating agents suchas dialkylaluminum alkoxides to generate the desired alkylmetallocene insitu. Reactions of this type are described for example in WO 95/10546.

[0082] Metallocene structures in this specification are to beinterpreted broadly, and include structures containing 1, 2, 3 or 4 Cpor substituted Cp rings. Thus metallocenes suitable for use in thisinvention can be represented by the Formula I:

B_(a)Cp_(b)ML_(c)X_(d)  (I)

[0083] where Cp independently in each occurrence is acyclopentadienyl-moiety-containing group which typically has in therange of 5 to about 24 carbon atoms; B is a bridging group or ansa groupthat links two Cp groups together or alternatively carries an alternatecoordinating group such as alkylaminosilylalkyl, silylamido, alkoxy,siloxy, aminosilylalkyl, or analogous monodentate hetero atom electrondonating groups; M is a d- or f-block metal atom; each L is,independently, a leaving group that is bonded to the d- or f-block metalatom and is capable of forming a stable co-product on interaction with aproton from a hydroxyaluminoxane; X is a group other than a leavinggroup that is bonded to the d- or f-block metal atom; a is 0 or 1; b isa whole integer from 1 to 3 (preferably 2); c is at least 2; d is 0or 1. The sum of b, c, and d is sufficient to form a stable compound,and often is the coordination number of the d- or f-block metal atom.

[0084] Cp is, independently, a cyclopentadienyl, indenyl, fluorenyl orrelated group that can π-bond to the metal, or ahydrocarbyl-, halo-,halohydrocarbyl-, hydrocarbylmetalloid-, and/orhalohydrocarbylmetalloid-substituted derivative thereof. Cp typicallycontains up to 75 non-hydrogen atoms. B, if present, is typically asilylene (—SiR₂—), benzo (C₆H₄<), substituted benzo, methylene (—CH₂—),substituted methylene, ethylene (—CH₂CH₂—), or substituted ethylenebridge. M is preferably a metal atom of Groups 4-6, and most preferablyis a Group 4 metal atom, especially hafnium, and most especiallyzirconium. L can be a divalent substituent such as an alkylidene group,a cyclometallated hydrocarbyl group, or any other divalent chelatingligand, two loci of which are singly bonded to M to form a cyclic moietywhich includes M as a member. In most cases L is methyl. X, if present,can be a leaving group or a non-leaving group, and thus can be a halogenatom, a hydrocarbyl group (alkyl, cycloalkyl, alkenyl, cycloalkenyl,aryl, aralkyl, etc.), hydrocarbyloxy, (alkoxy, aryloxy, etc.) siloxy,amino or substituted amino, hydride, acyloxy, triflate, and similarunivalent groups that form stable metallocenes. The sum of b, c, and dis a whole number, and is often from 3-5. When M is a Group 4 metal oran actinide metal, and b is 2, the sum of c and d is 2, c being atleast 1. When M is a Group 3 or Lanthanide metal, and b is 2, c is 1 andd is zero. When M is a Group 5 metal, and b is 2, the sum of c and d is3, c being at least 2.

[0085] Also incorporated in this invention are compounds analogous tothose of Formula I where one or more of the Cp groups are replaced bycyclic unsaturated charged groups isoelectronic with Cp, such asborabenzene or substituted borabenzene, azaborole or substitutedazaborole, and various other isoelectronic Cp analogs. See for exampleKrishnamurti, et al., U.S. Pat. No. 5,554,775 and 5,756,611.

[0086] In one preferred group of metallocenes, b is 2, i.e., there aretwo cyclopentadienylmoiety containing groups in the molecule, and thesetwo groups can be the same or they can be different from each other.

[0087] Another sub-group of useful metallocenes which can be used in thepractice of this invention are metallocenes of the type described in WO98/32776 published Jul. 30, 1998. These metallocenes are characterizedin that one or more cyclopentadienyl groups in the metallocene aresubstituted by one or more polyatomic groups attached via a N, O, S, orP atom or by a carbon-to-carbon double bond. Examples of suchsubstituents on the cyclopentadienyl ring include —OR, —SR, —NR₂, —CH═,—CR═, and —PR₂, where R can be the same or different and is asubstituted or unsubstituted C₁-C₁₆ hydrocarbyl group, a tri-C₁-C₈hydrocarbylsilyl group, atri-C₁-C₈hydrocarbyloxysilyl group, amixedC₁-C₈ hydrocarbyl and C₁-C₈ hydrocarbyloxysilyl group, a tri-C₁-C₈hydrocarbylgermyl group, a tri-C₁-C₈ hydrocarbyloxygermyl group, oramixed C₁-C₈ hydrocarbyl and C₁-C₈ hydrocarbyloxygermyl group.

[0088] Examples of metallocenes to which this invention is applicableinclude such compounds as:

[0089] bis(methylcyclopentadienyl)titanium dimethyl;

[0090] bis(methylcyclopentadienyl)zirconium dimethyl;

[0091] bis(n-butylcyclopentadienyl)zirconium dimethyl;

[0092] bis(dimethylcyclopentadienyl)zirconium dimethyl;

[0093] bis(diethylcyclopentadienyl)zirconium dimethyl;

[0094] bis(methyl-n-butylcyclopentadienyl)zirconium dimethyl;

[0095] bis(n-propylcyclopentadienyl)zirconium dimethyl;

[0096] bis(2-propylcyclopentadienyl)zirconium dimethyl;

[0097] bis(methylethylcyclopentadienyl)zirconium dimethyl;

[0098] bis(indenyl)zirconium dimethyl;

[0099] bis(methylindenyl)zirconium dimethyl;

[0100] dimethylsilylenebis(indenyl)zirconium dimethyl;

[0101] dimethylsilylenebis(2-methylindenyl)zirconium dimethyl;

[0102] dimethylsilylenebis(2-ethylindenyl)zirconium dimethyl;

[0103] dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dimethyl;

[0104] 1,2-ethylenebis(indenyl)zirconium dimethyl;

[0105] 1,2-ethylene bis(methylindenyl)zirconium dimethyl;

[0106] 2,2-propylidenebis(cyclopentadienyl)(fluorenyl)zirconiumdimethyl;

[0107] dimethylsilylenebis(6-phenylindenyl)zirconium dimethyl;

[0108] bis(methylindenyl)zirconium benzyl methyl;

[0109] ethylenebis[2-(tert-butyldimethylsiloxy)-1-indenyl]zirconiumdimethyl;

[0110] dimethylsilylenebis(indenyl)chlorozirconium methyl;

[0111] 5-(cyclopentadienyl)-5-(9-fluorenyl)1-hexene zirconium dimethyl;

[0112] dimethylsilylenebis(2-methylindenyl)hafnium dimethyl;

[0113] dimethylsilylenebis(2-ethylindenyl)hafnium dimethyl;

[0114] dimethylsilylenebis(2-methyl-4-phenylindenyl)hafnium dimethyl;

[0115] 2,2-propylidenebis(cyclopentadienyl)(fluorenyl)hafinium dimethyl;

[0116] bis(9-fluorenyl)(methyl)(vinyl)silane zirconium dimethyl;

[0117] bis(9-fluorenyl)(methyl)(prop-2-enyl)silane zirconium dimethyl;

[0118] bis(9-fluorenyl)(methyl)(but-3-enyl)silane zirconium dimethyl;

[0119] bis(9-fluorenyl)(methyl)(hex-5-enyl)silane zirconium dimethyl;

[0120] bis(9-fluorenyl)(methyl)(oct-7-enyl)silane zirconium dimethyl;

[0121] (cyclopentadienyl)(1-allylindenyl)zirconium dimethyl;

[0122] bis(1-allylindenyl)zirconium dimethyl;

[0123] (9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)zirconium dimethyl;

[0124] (9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyl)zirconiumdimethyl;

[0125] bis(9-(prop-2-enyl)fluorenyl)zirconium dimethyl;

[0126] (9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl)zirconiumdimethyl;

[0127] bis(9-(cyclopent-2-enyl)(fluorenyl)zirconium dimethyl;

[0128] 5-(2-methylcyclopentadienyl)-5(9-fluorenyl)-1-hexene zirconiumdimethyl;

[0129]1-(9-fluorenyl)-1-(cyclopentadienyl)-1-(but-3-enyl)-1-(methyl)methanezirconium dimethyl;

[0130] 5-(fluorenyl)-5-(cyclopentadienyl)-1-hexene hafnium dimethyl;

[0131] (9-fluorenyl)(1-allylindenyl)dimethylsilane zirconium dimethyl;

[0132]1-(2,7-di(alpha-methylvinyl)(9-fluorenyl)-1-(cyclopentadienyl)-1,1-dimethylmethanezirconium dimethyl;

[0133]1-(2,7-di(cyclohex-1-enyl)(9-fluorenyl))-1-(cyclopentadienyl)-1,1-methanezirconium dimethyl;

[0134] 5-(cyclopentadienyl)-5-(9-fluorenyl)-1-hexene titanium dimethyl;

[0135] 5-(cyclopentadienyl)-5-(9-fluorenyl)l-hexene titanium dimethyl;

[0136] bis(9-fluorenyl)(methyl)(vinyl)silane titanium dimethyl;

[0137] bis(9-fluorenyl)(methyl)(prop-2-enyl)silane titanium dimethyl;

[0138] bis(9-fluorenyl)(methyl)(but-3-enyl)silane titanium dimethyl;

[0139] bis(9-fluorenyl)(methyl)(hex-5-enyl)silane titanium dimethyl;

[0140] bis(9-fluorenyl)(methyl)(oct-7-enyl)silane titanium dimethyl;

[0141] (cyclopentadienyl)(1-allylindenyl) titanium dimethyl;

[0142] bis(1-allylindenyl)titanium dimethyl;

[0143] (9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)hafnium dimethyl;

[0144] (9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyl)hafniumdimethyl;

[0145] bis(9-(prop-2-enyl)fluorenyl)hafinium dimethyl;

[0146] (9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl)hafniumdimethyl;

[0147] bis(9-(cyclopent-2-enyl)(fluorenyl)hafnium dimethyl;

[0148] 5-(2-methylcyclopentadienyl)-5(9-fluorenyl)-1-hexene hafiiumdimethyl;

[0149] 5-(fluorenyl)-5-(cyclopentadienyl)-1-octene hafnium dimethyl;

[0150] (9-fluorenyl)(1-allylindenyl)dimethylsilane hafnium dimethyl;

[0151] (tert-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(1,3-pentadiene);

[0152] (cyclopentadienyl)(9-fluorenyl)diphenylmethane zirconiumdimethyl;

[0153] (cyclopentadienyl)(9-fluorenyl)diphenylmethane hafnium dimethyl;

[0154] dimethylsilanylene-bis(indenyl)thorium dimethyl;

[0155] dimethylsilanylene-bis(4,7-dimethyl-1-indenyl)zirconium dimethyl;

[0156] dimethylsilanylene-bis(indenyl)uranium dimethyl;

[0157] dimethylsilanylene-bis(2-methyl-4-ethyl-1-indenyl)zirconiumdimethyl;

[0158]dimethylsilanylene-bis(2-methyl-4,5,6,7tetrahydro-1-indenyl)zirconiumdimethyl;

[0159] (tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dimethyl;

[0160] (tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanechromium dimethyl;

[0161] (tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dimethyl;

[0162] (phenylphosphido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dimethyl; and

[0163] [dimethylsilanediylbis(indenyl)]scandium methyl.

[0164] In many cases the metallocenes such as referred to above willexist as racemic mixtures, but pure enantiomeric forms or mixturesenriched in a given enantiomeric form can be used.

[0165] A feature of this invention is that not all metallocenes canproduce compositions having the excellent catalytic activity possessedby the compositions of this invention. For example, in the absence of aseparate metal alkyl compound, bis(cyclopentadienyl)dichlorides of Zrcannot produce the compositions of this invention because the chlorideatoms are not capable of serving as leaving groups under the conditionsused in forming the compositions of this invention. Thus on the basis ofthe state of present knowledge, in order to practice this invention, itis desirable to perform preliminary tests with any given previouslyuntested metallocene to determine catalytic activity of the product ofreaction with a hydroxyaluminoxane. In conducting such preliminarytests, use of the procedures and reaction conditions of the Examplespresented hereinafter, or suitable adaptations thereof, is recommended.

[0166] In another embodiment of this invention, contrary to that whichwas previously known, it now surprisingly has been found thatrac-ethylene bis(1-indenyl)zirconium dimethyl also can be used toproduce a polymerization catalyst composition of this invention whichexhibits catalytic activity. Example 15 hereinafter illustrates thepreparation and use of this catalyst composition as an olefinpolymerization catalyst.

[0167] Reaction Conditions

[0168] To produce the catalytically active catalyst compositions of thisinvention the reactants, the d- or f-block metal compound, and thehydroxyaluminoxane that has either been freshly prepared or stored atlow temperature (e.g., -10° C or below) are brought together preferablyin solution form or on a support. The reaction between the hydroxy groupand the bond between the leaving group and the d- or f-block metal isstoichiometric and thus the proportions used should be approximatelyequimolar. The temperature of the reaction mixture is kept in the rangeof about −78 to about 160° C. and preferably in the range of about 15 toabout 30° C. The reaction is conducted under an inert atmosphere and inan inert environment such as in an anhydrous solvent medium. Reactiontimes are short, typically within four hours. When the catalystcomposition is to be in supported form on a catalyst support or carrier,the suitably dried, essentially hydrate-free support can be included inthe reaction mixture. However, it is possible to add the catalyst to thesupport after the catalyst composition has been formed.

[0169] When substituting for the hydroxyaluminoxane reactant in thesereactions, a composition in the form of one or more individual solidsformed from a hydroxyaluminoxane and a carrier material, the reactionconditions for producing the active catalyst compositions will be thesame as those taught in the preceding paragraph, with the additionalnote that use of such composition suspended in a viscous inert liquid(e.g., mineral oil) as previously discussed herein may be preferred incertain applications as the source of the hydroxyaluminoxane reactant.The presence of such viscous inert liquid can act to insulate theresulting activated catalyst composition from air or other reactants inthe surrounding environment, and can otherwise facilitate handling ofthe catalyst compositions. The use of the co-catalyst compositions ofmatter on carrier material in forming the active catalyst compositionare preferred over unsupported hydroxyaluminoxane, since it provides amore stable reactant (the hydroxyaluminoxane/carrier composition) interms of OH-decay as compared to unsupported hydroxyaluminoxane, whichin turn enables the use of lower amounts (on a molar basis) of thehydroxyaluminoxane/carrier composition to obtain at least the same levelof activation.

[0170] It should also be noted that, just as in the formation of theco-catalyst compositions from hydroxyaluminoxane and a carrier material,the catalysts may be formed by bringing together the metal compound andthe co-catalyst without isolating the co-catalyst from solution. Thus,for example, the metal compound may be mixed with the co-catalystcomposition in the same reaction vessel or zone in which the co-catalystcomposition is formed, and whether the co-catalyst is formed by bringingtogether a starting hydroxyaluminoxane and a carrier material, or bybringing together a starting aluminium alkyl, a carrier material in aninert solvent, and water under co-catalyst forming conditions. In otherwords, the metal compound may be brought together with a mixture inwhich the co-catalyst may be formed in order to form the activatedcatalyst composition in situ, whereupon the catalyst composition may beisolated and used or stored for later use as a polymerization catalyst.The reaction conditions for in situ formation of the active catalystcompositions should be the same as those taught above generally for theformation of the active catalyst compositions. Accordingly, anotherembodiment of this invention is the process which comprises bringingtogether, in an inert solvent, an aluminum alkyl and a carrier materialto form a first mixture, bringing together the first mixture and a watersource to form a second mixture in which a supported hydroxyaluminoxaneis formed, and then bringing the second mixture together with the d- orf-block metal compound to form a third mixture in which an activatedpolymerization catalyst on support is formed. If desired, the activatedcatalyst then may be isolated from the third mixture. This embodimentpresents a particularly economical way of producing the desired catalystin a supported and highly stable form.

[0171] Recovery of the Active Catalyst Compositions

[0172] Typically the active catalyst composition can be recovered fromthe reaction mixture in which it was formed simply by use of a knownphysical separation procedure. Since the reaction involved in theformation of the product preferably uses a metallocene having one or twomethyl groups whereby gaseous methane is formed as the coproduct, themetal-containing catalyst product is usually in a reaction mixturecomposed almost entirely of the desired catalyst composition and thesolvent used. This renders the recovery procedure quite facile. Forexample, where the product is in solution in the reaction mixture, thesolvent can be removed by stripping off the solvent under reducedpressure and at moderately elevated temperature. Often the residualproduct recovered in this manner is of sufficient purity that furtherpurification is not required. In the event the product is in the form ofsolids which precipitate from the solvent, or which are caused toprecipitate from the solution by the addition of a suitable non-solvent,physical solid-liquid separation procedures such as filtration,centrifugation, and/or decantation can be employed. The productrecovered in this manner is usually of sufficient purity that furtherpurification is not required. Whatever the method ofrecovery used, iffurther purification is needed or desired, conventional purificationsteps, such as crystallization can be used.

[0173] The product need not be recovered or isolated directly from theliquid reaction medium in which it was prepared. Instead, it can betransferred to another solvent, for example, by use of a solventextraction procedure or a solvent swap procedure whereby the product isremoved from the liquid phase in which it was produced and is thusdissolved in a different solvent. Although unnecessary, this newsolution can be subjected to still another solvent extraction, orsolvent swap, as many times as desired, recognizing of course that thelonger the product remains in solution the greater the opportunity forproduct degradation to occur. In any case referred to in this paragraph,the catalytically active product is recovered or isolated from asolution other than the liquid phase in which it was produced, and ismaintained in undissolved condition under dry, anhydrous conditions.

[0174] Storage of Recovered Active Catalyst Compositions

[0175] The recovered catalyst compositions of this invention can bestored in any suitable air-tight container either under vacuum or underan atmosphere of anhydrous inert gas, such as nitrogen, helium, argon,or the like. To protect against possible light-induced degradation, thecontainer is preferably opaque or rendered opaque toward lighttransmission and/or the package containing the catalyst composition iskept in a suitable dark storage area. Likewise it is desirable to storethe product in locations that will not become excessively hot. Exposureto storage temperatures of up to about 30° C. typically will cause nomaterial loss in activity, but naturally the effect of temperatureslikely to be encountered during storage should be determined for anygiven catalyst where such information has not previously beenascertained.

[0176] The length of time during which the recovered active catalystcomposition is stored can be as short as a minute or less. For example,the active catalyst composition could be produced in an appropriateamount at the site of the polymerization and immediately upon isolationcould be directly transferred to the polymerization reaction vessel. Thestorage period in such case could be very short, namely the time betweenisolation of the active catalyst composition and commencement of its useas the catalyst in the polymerization. On the other hand, the storageperiod can be substantially longer provided that the storage occursunder the appropriate conditions at all times during the storage. Forexample, the active catalyst composition could be produced, placed in asuitable air-tight, moisture-resistant vessel or container under a dry,anhydrous atmosphere promptly after its isolation, and then maintainedin inventory in a suitable air-tight, moisture-resistant vessel orcontainer under a dry, anhydrous atmosphere, all at the site of itsmanufacture, and with these steps being conducted such that the amountof exposure to air or moisture, if any, is kept at all times to such aminimal amount as not to adversely affect the activity of the catalystcomposition. All or a portion of such stored active catalyst compositioncould then be shipped under these same conditions to another site,typically the site where its use as a polymerization catalyst is to takeplace. And after reaching the site where the composition is to be usedas a catalyst, the composition could then again be kept in inventoryunder the same or substantially the same type of suitable storageconditions at that site until portions of the catalyst composition areput to use as a catalyst. In such a case the overall storage periodcould be very long, e.g., as long as the particular catalyst compositionretains suitable catalytic activity. Thus the period of storage isdiscretionary and is subject to no numerical limitation as it can dependon such factors as the extent of care exercised in the various steps towhich the stored product is subjected during storage, the conditionsexisting or occurring during the storage, and so on. Thus as a practicalmatter the period of time of the storage can be the period of timeduring which the catalyst does not lose its activity or effectivenesswhen used as a polymerization catalyst.

[0177] The catalyst compositions of this invention can be stored inisolated form, or in various other undissolved forms. For example, afterrecovery, the active catalyst composition can be mixed under dry,anhydrous conditions with dry inert materials such as calcinedparticulate or powdery silica, alumina, silica-alumina, clay,montmorillonite, diatomaceous earth, or like substance, and theresultant dry blend can be stored under appropriate dry, anhydrousconditions. Similarly, after recovery, the active catalyst compositioncan be mixed under dry, anhydrous conditions with other kinds of dryinert materials such as chopped glass fibers, glass beads, carbonfibers, metal whiskers, metal powders, and/or other materials commonlyused as reinforcing fillers for polymers, and the resultant blends canthen be stored under appropriate dry, anhydrous conditions. In apreferred embodiment, after recovery, the active catalyst composition issupported on a dry catalyst support material such as calcined silica,calcined silica-alumina, calcined alumina, particulate polyethylene,particulate polypropylene, or other polyolefin homopolymer or copolymerunder anhydrous air-free conditions using known technology, and theresultant supported catalyst composition is then stored underappropriate dry, anhydrous conditions. In case anyone needs to be toldwhat “appropriate conditions” are, they include not exposing the storedcatalyst composition to such high temperatures as would causedestruction of the catalyst or its catalytic activity, and not exposingthe stored catalyst to light wave energy or other forms of radiation ofsuch type or magnitude as would cause destruction of the catalyst or itscatalytic activity. Here again, this disclosure as any patentdisclosure, should be read with at least a little common sense, ratherthan with legalistic word play in mind.

[0178] The catalyst compositions of this invention are particularlystable, as they typically will be able to be maintained in a dry stateunder anhydrous or substantially anhydrous conditions and at atemperature in the range of about 5 to about 70° C., more preferably inthe range of about 10 to about 60° C., and most preferably in the rangeof about 15 to about 35° C., for a period of time of at least about 24hours, more preferably for at least about 48 hours, and most preferablyat least about 72 hours, without losing fifty percent (50%) or more ofits catalytic activity. It should be appreciated that such catalyticactivity would be measured in terms of grams of polymer per gram ofcatalyst composition per hour, samples being compared using identicalpolymerization reaction conditions.

[0179] Polymerization Processes Using Catalysts of this Invention

[0180] The catalyst compositions of this invention can be used insolution or deposited on a solid support. Depositing upon a carrier orsolid support is particularly preferred. When used in solutionpolymerization, the solvent can be, where applicable, a large excessquantity of the liquid olefinic monomer. Typically, however, anancillary inert solvent, typically a liquid paraffinic or aromatichydrocarbon solvent is used, such as heptane, isooctane, decane,toluene, xylene, ethylbenzene, mesitylene, or mixtures of liquidparaffinic hydrocarbons and/or liquid aromatic hydrocarbons. When thecatalyst compositions of this invention are supported on a carrier, thesolid support or carrier can be any suitable particulate solid, andparticularly a porous support such as talc, zeolites, or inorganicoxides, or resinous support material such as polyolefins. Preferably,the support material is an inorganic oxide in finely divided form.

[0181] Suitable inorganic oxide support materials which are desirablyemployed include metal oxides such as silica, alumina, silica-aluminaand mixtures thereof. Other inorganic oxides that may be employed eitheralone or in combination with the silica, alumina or silica-alumina aremagnesia, titania, zirconia, and like metal oxides. Other suitablesupport materials are finely divided polyolefins such as finely dividedpolyethylene.

[0182] Polymers can be produced pursuant to this invention byhomopolymerization of polymerizable olefins, typically 1-olefins (alsoknown as α-olefins) such as ethylene, propylene, 1-butene, orcopolymerization of two or more copolymerizable monomers, at least oneof which is typically a 1-olefin. The other monomer(s) used in formingsuch copolymers can be one or more different 1-olefins and/or adiolefin, and/or a polymerizable acetylenic monomer. Olefins that can bepolymerized in the presence of the catalysts of this invention includeα-olefins having 2 to 20 carbon atoms such as ethylene, propylene,1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, and 1-octadecene. Other suitable monomersfor producing homopolymers and copolymers include styrenic monomers,e.g., styrene, ar-methylstyrenes, alpha-methylstyrene,ardimethylstyrenes, ar-ethylstyrene, 4-tert-butylstyrene, andvinylnaphthalene. Still other suitable monomers include polycyclicmonomers. Illustrative examples of suitable polycyclic monomers include2-norbomene, 5-methyl-2-norbomene, 5-hexyl-2-norbornene,5-decyl-2-norbomene, 5-phenyl-2-norbornene, 5-naphthyl-2-norbomene,5-ethylidene-2-norbomene, vinylnorbomene, dicyclopentadiene,dihydrodicyclopentadiene, tetracyclododecene, methyltetracyclododecene,tetracyclododecadiene, dimethyltetracyclododecene,ethyltetracyclododecene, ethylidenyl tetracyclododecene,phenyltetracyclododecene, trimers of cyclopentadiene (e.g., symmetricaland asymmetrical trimers). Copolymers based on use of isobutylene as oneof the monomers can also be prepared. Normally, the hydrocarbon monomersused, such as 1-olefins, diolefins and/or acetylene monomers, willcontain up to about 10 carbon atoms per molecule. Preferred 1-olefinmonomers for use in the process include ethylene, propylene, 1-butene,3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. It isparticularly preferred to use supported catalysts of this invention inthe polymerization of ethylene, or propylene, or ethylene and at leastone C₃-C₈ 1-olefin copolymerizable with ethylene. Typical diolefinmonomers which can be used to form terpolymers with ethylene andpropylene include butadiene, hexadiene, norbomadiene, and similarcopolymerizable diene hydrocarbons. 1-Heptyne and 1-octyne areillustrative of suitable acetylenic monomers which can be used.

[0183] Polymerization of ethylene or copolymerization with ethylene andan α-olefin having 3 to 10 carbon atoms may be performed in either thegas or liquid phase (e.g. in a diluent, such as toluene, or heptane).The polymerization can be conducted at conventional temperatures (e.g.,0° to 120° C.) and pressures (e.g., ambient to 50 kg/cm²) usingconventional procedures as to molecular weight regulations and the like.

[0184] The heterogeneous catalysts of this invention can be used inpolymerizations conducted as slurry processes or as gas phase processes.By “slurry” is meant that the particulate catalyst is used as a slurryor dispersion in a suitable liquid reaction medium which may be composedof one or more ancillary solvents (e.g., liquid aromatic hydrocarbons,etc.) or an excess amount of liquid monomer to be polymerized in bulk.Generally speaking, these polymerizations are conducted at one or moretemperatures in the range of about 0 to about 160° C., and underatmospheric, subatmospheric, or superatmospheric conditions.Conventional polymerization adjuvants, such as hydrogen, may be employedif desired. Preferably polymerizations conducted in a liquid reactionmedium containing a slurry or dispersion of a catalyst of this inventionare conducted at temperatures in the range of about 40 to about 110° C.Typical liquid diluents for such processes include hexane, toluene, andlike materials. Typically, when conducting gas phase polymerizations,superatmospheric pressures are used, and the reactions are conducted attemperatures in the range of about 50 to about 160° C. These gas phasepolymerizations can be performed in a stirred or fluidized bed ofcatalyst in a pressure vessel adapted to permit the separation ofproduct particles from unreacted gases. Thermostated ethylene,comonomer, hydrogen and an inert diluent gas such as nitrogen can beintroduced or recirculated to maintain the particles at the desiredpolymerization reaction temperature. An aluminum alkyl such astriethylaluminum may be added as a scavenger ofwater, oxygen and otherimpurities. In such cases the aluminum alkyl is preferably employed as asolution in a suitable dry liquid hydrocarbon solvent such as toluene orxylene. Concentrations of such solutions in the range of about 5×10⁻⁵molar are conveniently used. But solutions of greater or lesserconcentrations can be used, if desired. Polymer product can be withdrawncontinuously or semi-continuously at a rate that maintains a constantproduct inventory in the reactor.

[0185] The catalyst compositions of this invention can also be usedalong with small amounts of hydrocarbylborane compounds such astriethylborane, tripropylborane, tributylborane, tri-sec-butylborane.When so used, molar A/B ratios in the range of about 1/1 to about 1/500can be used.

[0186] Because of the high activity and productivity of the catalysts ofthis invention, the catalyst levels used in olefin polymerizations canbe less than previously used in typical olefin polymerizations conductedon an equivalent scale. In general, the polymerizations andcopolymerizations conducted pursuant to this invention are carried outusing a catalytically effective amount of a novel catalyst compositionof this invention, which amount may be varied depending upon suchfactors such as the type of polymerization being conducted, thepolymerization conditions being used, and the type of reaction equipmentin which the polymerization is being conducted. In many cases, theamount of the catalyst of this invention used will be such as to providein the range of about 0.000001 to about 0.01 percent by weight of d- orf-block metal based on the weight of the monomer(s) being polymerized.

[0187] After polymerization the product polymer can be recovered fromthe polymer by any suitable means. When conducting the process inslurry, dispersion or bulk monomer (e.g. liquid propylene) media theproduct is typically recovered and dried by a physical separationtechnique using a device such as a wiped film evaporator (WFE) orsimilar distillative techniques. Alternatively the polymer can beseparated by filtration or decantation methods. When conducting theprocess as a gas phase polymerization the resulting polymer is freedfrom residual monomer by any suitable means such as purging withnitrogen, with or without additional heating. When the catalysts areemployed in solution polymerization processes the product is againrecovered and dried by any suitable physical separation technique,usually involving evaporation. Alternatively the polymer can beprecipitated from solution by adding a suitable non-solvent (e.g.heptane, iso-propanol, acetone) and then recovered by any suitablephysical separation technique followed by drying.

[0188] Due to the high productivity of the catalysts it is not usuallynecessary to deactivate the catalyst nor to extract catalyst residuesprior to recovering the product polymer. However if desired the catalystcan be deactivated in the conventional manner by applying a short-stopsuch as an alcohol (e.g. iso-propanol), oxygen, carbon monoxide, carbondioxide or water or mixtures thereof. Furthermore, if required thecatalyst residues and other impurities (such as less volatile monomers)can be removed by washing with one or more suitably volatile solventssuch as iso-propanol, iso-butanol, acetone, methylethylketone, aliphaticor aromatic hydrocarbons.

[0189] When preparing polymers pursuant to this invention conditions maybe used for preparing unimodal or multimodal polymer types. For example,mixtures of catalysts of this invention formed from two or moredifferent metallocenes having different propagation and termination rateconstants for ethylene polymerizations can be used in preparing polymershaving broad molecular weight distributions of the multimodal type.

[0190] Experimental Section

[0191] The following Examples are presented for purposes of illustrationand not limitation. All operations of these Examples were carried outunder nitrogen either in a drybox with below 1 ppm oxygen or usingstandard Schlenk line techniques. Methylaluminoxane (MAO),triisobutylaluminum (TIBA), triethylaluminum (TEA), were commercialproducts of Albemarle Corporation and used as received. Reagentsbenzylmagnesium chloride and MeLi with LiBr were purchased from Aldrichand used as received. Toluene, ethylene, propylene, and nitrogen used inthe polymerization reactions were purified by passing through a seriesof three cylinders: molecular sieves, Oxyclear oxygen absorbent, andalumina. Ethylene and propylene were polymer grade from Matheson.Toluene for catalyst preparation and spectros-copy studies was Aldrichanhydrous grade and was distilled from sodium/benzophenone ketyl. Hexanewas Aldrich anhydrous grade and stored over Na/K alloy. The metallocenesused in these Examples were prepared according to procedures given inthe literature. Thus Cp₂ZrMe₂ was prepared using the method of Samuel,et al., J. Am. Chem. Soc., 1973, 95, 6263;racdimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride using themethod of Spaleck, et al., Angew. Chem., Int. Ed. Engl., 1992, 31, 1347,and Winter, et al. U.S. Pat. No. 5,145,819; andbis(1-methyl-3-n-butyl-cyclopentadienyl)zirconium dichloride using themethod of Lee, et al., Canadian Pat. No. 2,164,914, July 1996. TheFT-infrared spectra of FIGS. 1, 2 and 3 were recorded on a NicoletMagna-IR 750 spectrometer with 32 scans and 2 cm⁻¹ resolution using 0.5mm NaCl cells. The absorption of hexane was compensated by subtractionwith a reference hexane spectrum acquired from the same cell. The UV-Visspectra were recorded in the 290-700 run region on a Varian Cary 3Espectrometer. Quartz cuvettes of 1 cm pathlength were used. Diffusereflectance infrared fourier transform spectroscopy (DRIFTS) use aNicolet Magna 750 FTIRbench equipped with a “Collector” diffusereflectance accessory from spectra-Tech with a high temperature/highpressure sample chamber. The DRIFTS spectra (FIG. 8) were obtained at 4cm-1 resolution and 128 scans. The molecular weight and molecular weightdistribution were determined by gel permeation chromatography whichincorporated three different modes of detection including differentialrefractive index (Polymer Labs), laser light scattering (PrecisionDetectors) and differential pressure viscometry (Viscotek Corporation).The chromatographic instrument was a Polymer Labs 210 using1,2,4-trichlorobenezene as the eluting solvent at 150° C. A series oflinear mixed bed GPC columns were used to perform the separation and thedata was collected and analyzed using Viscotek's TriSEC softwarepackage. The samples were dissolved in the tricholorbenzene for 2-4hours at 150° C. at a concentration of approximately 2000 rpm.MFI, meltflow index, was determined by the ASTM D1238 method.

EXAMPLE 1 Rac-dimethylsilylbis(2-methylindenyl)zirconium Dimethyl(MET-A)

[0192] Rac-dimethylsilylbis(2-methylindenyl)zirconium dichloride (5.03g, 10.55 mmol) was suspended in 100 g of toluene. The orange slurry washeated in an oil bath to 40° C. Most of the orange-yellow metalloceneremained undissolved. MeLi/LiBr (5.87 wt % in ether, 7.78g) was addeddropwise over two hours. The solution became amber/yellow and the solidslightened. The reaction was allowed to cool to ambient temperature andstir overnight. Analysis of the reaction showed 9.3 mol % of mono-methylintermediates. Additional aliquots of MeLi/LiBr (1.66 g) were addeddropwise until the monomethyl intermediates were reduced to less thantwo mol %. Approximately a quarter of the solvent was removed in vacuoand then the lithium salts were filtered on a medium frit and washedwith 20 mL of toluene. The combined filtrates were concentrated invacuo. A yellow crystalline solid formed. The slurry was cooled to −20°C. The yellow crystals were filtered on a coarse frit. After drying invacuo, the yield of rac-dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl was 3.20 g (70%).

EXAMPLE 2 Bis(1-butyl-3-methylcyclopentadienyl)zirconium Dimethyl(MET-B)

[0193] Bis(1-butyl-3,4methylcyclopentadienyl)zirconium dichloride(2.71g,6.26 mmol)was dissolved in 21.4 g of toluene. Low-halide MeLi (˜1.5 M inether, 8.0 mL) was added dropwise at ambient temperature. A white solidformed immediately. The reaction was allowed to stir for 1.5 hours.Analysis of the reaction showed 3.5 mol % of mono-methyl intermediate.An additional aliquot of MeLi (0.4 mL) was then added to consume themonomethyl intermediate. After stirring overnight, the supernatantliquid was reanalyzed to verify that the reaction was complete. Theslurry was filtered on a medium frit and the solvent was removed invacuo. A light yellow liquid ofbis(1-butyl-3-methyl-cyclopentadienyl)-zirconium dimethyl remained (2.13g, 87% yield).

EXAMPLE 3 Synthesis of Hydroxyisobutylaluminoxane (HO-IBAO)

[0194] The reaction was carried out in a 1-L, three-necked,round-bottomed Morton flask equipped with a thermometer, an outletconnected to a Schlenk line, and a rubber septum through which water wasadded via a syringe needle. To this flask containing a solution oftriisobutylaluminum (98.4 g, 492.4 mmol) in hexane (276.4 g) withvigorous magnetic stirring was added degassed water (8.85 g, 491.4 mmol)using a syringe pump over a period of 65 minutes. The temperature wasmaintained at between -5 and 0° C. by applying a dry ice bath (withoutacetone) and by adjusting water addition speed. After the water additionwas complete, the solution was stirred for an additional ten minutes (oruntil the exothermic reaction subsided, which usually lasts about 5-10minutes after completion ofwater addition), stripped of dissolvedisobutane and some hexane under vacuum at a temperature somewhat belowambient, transferred, and stored in a −10° C. freezer in a drybox. Thesolution weighed 252.2 g and was determined by analysis to have a wt %Al of 5.15.

EXAMPLE 4 Synthesis of Deuteroxyisobutylaluminoxane (DO-IBAO)

[0195] The procedure of Example 3 was repeated with the exception thatan equivalent amount of D₂O was used in place of the water and theoperation was conducted with similar amounts of the reactants.

EXAMPLE 5 Characterization of HO-IBAO by IR-Spectroscopy

[0196] The presence of hydroxyl groups in the product solution ofExample 3 was indicated by an infrared spectrum (see FIG. 1) taken thenext day. Initially, there are two types of hydroxyl groups detected at3615 cm⁻¹ (major) and 3695 cm⁻¹ (minor), respectively. At roomtemperature, both are unstable particularly the major one. The stabilitystudy was carried out with another reaction solution in hexane (Al wt%=3.55, H₂O/Al=1.00). The liquid cuvette was left in the IR chamber atambient temperature and spectra were recorded at the indicated intervals(see FIG. 2). The last spectrum taken after two days at ambienttemperature, revealed possibly two additional OH frequencies at 3597cm⁻¹ and 3533 cm⁻¹. The stability of the hydroxyls groups depends on anumber of factors. For instance, the hydroxyl groups can be preservedfor a much longer time if the solution is kept at a lower temperature,or if added tetrahydrofuran which stabilizes the hydroxyls both byforming hydrogen-bonds, and by coordinating to aluminum sites; or byusing a higher hydrolysis ratio (hydroxyls are more stable in IBAO ofwater/Al=1.00 than in IBAO of water/Al=0.90).

[0197] As indicated by Example 4, the hydroxyl groups can be replaced bydeuteroxy groups by hydrolyzing TIBA with D₂O. A new IR band assignableto OD stretching appeared at 2665 cm⁻¹ corresponding to the 3615 cm⁻¹band for OH stretching (the corresponding OD band for the 3695 cm⁻¹stretching is not seen, presumably obscured by large C—H bands nearby).The ratio of two frequencies (n_(OH)/n_(OD)=1.356) indicates that thisOH or OD group is free or not engaged in any intra or intermolecularhydrogen bonding (the theoretical value is 1.35 which fallssystematically as the strengths of the hydrogen bond increases; see L.J. Bellamy, The Infrared Spectra of Complex Molecules, Volume Two,Second Edition, 1980, page 244, Chapman and Hall). Deuterated isobutane,(CH₃)₂CHCH₂D, a by-product of the hydrolysis reaction, was also detectedby IR as two equally intense bands at 2179 cm⁻¹ and 2171 cm⁻¹,respectively.

[0198] To enable correlation between IR absorbance and hydroxy contentof HO-IBAO, a quantitative determination of hydroxy content wasperformed (Example 6). In the absence of a model compound with knownhydroxy content, IR spectroscopy provides only qualitative information.

EXAMPLE 6 Quantification of Hydroxy Content in HO-IBAO; Benzyl GrignardMethod

[0199] To a cold, vigorously stirred HO-IBAO solution (5.52 g solution,10 mmol Al) with a 4.89 wt % Al and an IR absorbance of 0.557 for the3616 cm⁻¹ band was added a 2-M solution of benzylmagnesium chloride inTHF (2.0 ml, 4 mmol). The mixture quickly reacted becoming two layersand was stirred at ambient temperature for 90 minutes. After that, theresulting suspension was vacuum distilled at temperatures up to 50° C.over one hour and all volatiles were trapped in a flask cooled by aliquid nitrogen bath. The amount of toluene in the collected liquid wasdetermined by GC (with a known amount of pentadecane added as aninternal reference) to be 0.66 mmol, which corresponds to 6.6 OH groupsfor every 100 Al atoms.

[0200] The mechanism as depicted in Equation (2) above was proved by theuse of two different experiments, one involving deuterium labeling andGC-mass spectographic analysis (Examples 7 and 8), and the otherinfra-red analysis (Example 7).

EXAMPLE 7 Verification of Novel Metallocene Activation Mechanism;HO-IBAO Functions as a Brønsted Acid

[0201] Use of Deuterium-Labeled Reactant (DO-IBAO) with UnbridgedMetallocene. Into a 30-mL round-bottomed flask containing a coldsolution of deuteroxyisobutylaluminoxane (DO-IBAO) (OD stretching at2665 cm⁻¹, about 5-7 OD for every 100 Al) (3.31 wt % Al, 9.26 gsolution, 11.4 mmol Al) prepared by hydrolyzing the TIBA with D₂O wasadded solid bis(cyclopentadienyl)zirconium dimethyl (Cp₂ZrMe₂) (33 mg,0.13 mmol). The flask was immediately closed with a gas tight septum toprevent escape of any gaseous products. The volume of the solution wasca. 15 mL which left about another 15 mL of headspace in the flask. Ittook about 2-3 minutes for the metallocene solids to dissolve completelyto give a light yellow solution. After stirring for 85 minutes atambient temperature, a gaseous sample withdrawn from the head space ofthe flask was subjected to GC-Mass Spec analysis which showed acomposition of 9.1 mol % CH₃D and 90.9 mol % N₂. In other words, 1.37 mLof the 15-mL headspace was CH₃D, which corresponds to 43% of thetheoretical amount predicted by the reaction of Equation (2) above. Theamount of CH₃D remained dissolved in the solution was not determined.(In fact, if the solution was cooled to −10 to −20° C., CH₃D in theheadspace became too little to be detectable by GC-Mass Spec).

EXAMPLE 8 Verification of Novel Metallocene Activation Mechanism;HO-IBAO Functions as a Brønsted Acid

[0202] Use of Deuterium-Labeled Reactant (DO-IBAO) with BridgedMetallocene. This reaction was carried out analogously to Example 7above except that the reactants wererac-dimethylsilylbis(2-methyl-1-indenyl)zirconium dimethyl (45 mg, 0.103mmol) andDO-IBAO (12.23 g, 15.0 mmol Al) and the flask contained about19-mL of solution and 11-mL of headspace. The GC-Mass Spec analysisshowed a 4.8 mol % of CH₃D in the headspace, which corresponds to 21% ofthe theoretical amount. The lower percentage reflects the fact that theflask had less headspace and more solution volume for CH₃D to dissolvein.

EXAMPLE 9 Verification of Novel Metallocene Activation Mechanism;HO-IBAO Functions as a Brønsted Acid

[0203] Use of Infra-Red Analysis of Product from HO-IBAO and aMetallocene. To a cold, freshly prepared HO-IBAO (3.0 mmol Al, IRspectrum shown in FIG. 3 top) in hexane was added soliddimethylsilylbis(methylindenyl)zirconium dimethyl (0.1 mmol, Al/Zr=30).After stirring at ambient temperature for 30 minutes, the resulting deepred-brown solution was taken a IR spectrum shown in FIG. 3 bottom.Separately, another portion of the same cold HO-IBAO solution wasallowed to stand at ambient temperature for 30 minutes and its IRspectrum was taken immediately thereafter (shown in FIG. 3 middle). Itis clear from this set of three spectra that the reaction betweenHO-IBAO and the metallocene results in a rapid disappearance of thehydroxyl groups in IBAO, which cannot be accounted for by the slowerself-consumption during the same period.

EXAMPLE 10 UV-Vis Spectra ofrac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl+Hydroxy IBAOWith Varying Al/Zr Ratios

[0204] The reaction between hydroxy IBAO and methylated metallocene canbe readily monitored by UV-Vis. It has been reported that theligand-to-metal charge transfer (LMCT) bands undergo a characteristicbathochromic shift (shorter to longer wavelength) upon converting from aneutral metallocene (catalyst precursor) to a metallocenium cation(active catalyst) by an activator (Siedle, et al., Macromol Symp., 1995,89, 299; Pieters, et al., Macromol. Rapid Commun., 1995, 16, 463). Forrac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl, an LMCT band(see FIG. 4-solid) appearing at 394 nm (λ_(max), 4710 M⁻¹cm⁻¹) serves asa convenient probe to measure the progress of the activation reaction.As shown in FIG. 4-dotted, the more hydroxy IBAO is used, the more thestarting metallocene is consumed and the more adsorption is observed inthe longer wavelength region. It is clear from the spectra that an Al/Zrratio of 21 is almost enough to activate all of the metallocene.

[0205] As reference to FIG. 5 shows, this spectroscopy tool is alsouseful for measuring the effectiveness of a metallocene activator. Thus,a hydroxy-depleted isobutylaluminoxane (aged for three months at ambienttemperature, and indicated by IR to contain no detectable amount ofhydroxyl groups), hardly reacted withrac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl even at a higherAl/Zr ratio of 50. See FIG. 5, middle. Although the metallocene reactswith the tetraisobutyldialuminoxane (TIBAO) (formed using a water/Alratio of 0.50 and used at an Al/Zr ratio of 5000), little bathochromicshift occurred, indicating formation of virtually no active catalystformation. See FIG. 5, bottom. This observation of lack of formation ofactive catalyst was confirmed by the polymerization run described inComparative Example G, below.

[0206] The following examples (Examples 11-14 and Comparative ExamplesA-G) illustrate the highly advantageous results achievable using thepolymerization reactions of this invention.

EXAMPLE 11

[0207] The hydroxy IBAO used in this run had 6.16. wt % Al and had beenstored in a freezer at −10° C. in drybox for six days. The IR spectrumshowed an absorbance of 0.458 for the 3623 cm⁻¹ OH band, whichcorresponds essentially to an average of 4.2 OH groups per 100 Al atoms.

[0208] Polymerization of propylene was carried out in a 2-L stainlesssteel oil-jacketed reactor which had previously been heated to 100° C.under vacuum for one hour. After the reactor was charged with purifiedtoluene (600 mL) and propylene (400 mL), a 2-mL solution of 1% TIBA inhexane was injected into the reactor and the mixture was stirred at 50°C. for 5 minutes. After that polymerization was initiated by injecting acatalyst solution of rac-dimethylsilylbis(2-methylindenyl)zirconiumdimethyl (2 μmol) and hydroxy IBAO (50 μmol, Al/Zr=25) in 3 mL oftoluene which had previously been allowed to stand at ambienttemperature for one hour. The mixture was stirred at 800 rpm. Thetemperature immediately began to rise from 50° C. to peak at 74° C. 9minutes later. No make-up propylene was added. After ten minutes ofreaction, the unreacted propylene was quickly vented to stop thepolymerization. After adding methanol (>1000 mL), filtering, and dryingthe solids under vacuum at 100° C. overnight, 101 g of isotacticpolypropylene was isolated; polymer properties: M.P. (onset of secondmelt): 146.3° C.; Melt Flow Index (MFI) (230° C./5 kg): 40.68 (g/10min); mmmm %: 93.9%; Isotactic Index: 97.3%.

EXAMPLE 12

[0209] This polymerization of propylene used an HO-IBAO which wasindicated by IR analysis to contain an average of 4.0 OH groups per 100Al atoms. The materials and procedure were as in Example 11 except thatan Al/Zr ratio of 50, and more toluene (800 mL) were used. Yield: 127 g;M.P.(onset of second melt): 144.9° C.; MFI (230° C./5 kg): 87.97 (g/10min); mmmm %: 93.1%; Isotactic Index: 97.4%.

EXAMPLE 13

[0210] This HO-IBAO used in this polymerization was indicated by IRanalysis to contain and average of 3.2 OH groups per 100 Al atoms. Thematerials and procedure were as in Example 11 except that an Al/Zr ratioof 30, and more toluene (800 mL) were used. Yield: 88.6 g.; M.P.(onsetof second melt): 146.9° C.; MFI (230° C./5 kg): 56.28 (g/10 min); mmmm%: 93.1%; Isotactic Index: 96.9%; Molecular weight (via GPC):Mw=167,776, Mn=76,772, Mw/Mn=2.19.

COMPARATIVE EXAMPLE A

[0211] The procedure of Example 11 was repeated, except that thecatalyst solution was rac-dimethylsilylbis(2-methylindenyl)zirconiumdimethyl (1.0 μmol) and conventional methylaluminoxane (MAO) (1.0 mmol,Al/Zr=1000) in toluene, and no TIBA was used as scavenger. Compared toExample 11, this propylene polymerization reaction was much lessexothermic, taking awholehourofreaction fortemperatureto rise from 50°C. to 81° C.; Yield: 146 g; M.P.(onset ofsecondmelt): 144.4° C.; MFI(230° C./5 kg): 79.90 (g/10 min); mmmm %: 92.2%; Isotactic Index: 96.5%;Molecular weight (via GPC): Mw=197,463, Mn=84,967, Mw/Mn=2.32.

COMPARATIVE EXAMPLE B

[0212] This polymerization was carried out in a 300-mL Parr reactorequipped with an internal cooling coil. Into the reactor in drybox wascharged with a catalyst solution ofrac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl (0.3 μmol) andMAO (1.5 mmol, Al/Zr=5000) in about 150 mL of dry toluene. The reactorwas sealed, transferred, and heated to 68° C. With stirring set at 800rpm, the polymerization was initiated by pressing in 28 g of liquidpropylene. The temperature was maintained at 70° C. by applying coolingintermittently. After 10 minutes, the polymerization was quenched byadding MeOH. Yield: 7.2 g. M.P.(onset of second melt): 145.9° C.

COMPARATIVE EXAMPLE C

[0213] The procedure was as in Example 11 except that the catalystsolution was rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl(1.0 μmol) and MAO (0.1 mmol, Al/Zr=100) in toluene. No exothermicreaction was observed. The reaction after one hour produced only a traceof solid polymer.

COMPARATIVE EXAMPLE D

[0214] This polymerization used TIBAO (tetraisobutylaluminoxane) made byhydrolyzing TIBA with a half equivalent of water (water to aluminumratio=0.5) and the IR spectrum of the product showed no evidence of anyOH group present. The procedure was as in Example 11 except that anAl/Zr ratio of 100 was used. No polymerization activity was observed.

COMPARATIVE EXAMPLE E

[0215] This polymerization was carried out in a 300-mL Parr reactor withprocedure analogous to that in Comparative Example D except that theAl/Zr ratio was 5000, reaction temperature was 70° C., and reaction timewas 20 minutes. Only 0.91 g of polymer was isolated.

COMPARATIVE EXAMPLE F

[0216] This polymerization used hydroxyisobutylaluminoxane indicated byIR analysis to contain an average of 5.3 OH groups per 100 μl atoms. Theprocedure was as in Example 11 except that an Al/Zr ratio of 3000 wasused. The polymerization was initially as exothermic as that in Example11. However, when the temperature reached 63° C. (from 50° C.) after 4minutes of reaction, the exothermic reaction suddenly ceased and thetemperature quickly reversed its rising trend, returning to 52° C. inthe next 6 minutes. The reaction was allowed to continue for anadditional 20 minutes. Yield: 38.6 g. M.P.(onset of second melt): 148.0°C.; MFI (230° C./5 kg): 16.67 (g/10 min); mmmm %: 92.6%; IsotacticIndex: 96.8%.

COMPARATIVE EXAMPLE G

[0217] This polymerization used hydroxyisobutylaluminoxane indicated byIR analysis to contain an average of 3.8 OH groups per 100 Al atoms. Theprocedure was as in Example 11 except that the metallocene used wasrac-dimethylsilylbis(2-methylindenyl)zirconium dichloride not thedimethyl analog. In addition, an Al/Zr ratio of 50, and more toluene(800 mL) were used. No reaction was observed.

EXAMPLE 14

[0218] This ethylene polymerization used hydroxyisobutylaluminoxane madeby hydrolyzing TIBA with 0.9 equivalent ofwater. This HO-IBAO wasindicated by IR analysis to contain an average of 1.5 OH groups per 100Al atoms at the time of use. The procedure was as in Example 11 with thefollowing modifications: The catalyst used was a mixture ofbis(1-butyl-3-methylcyclopentadienyl)zirconium dimethyl (2 μmol) andhydroxyisobutylaluminoxane (200 μmol), and was allowed to stand atambient temperature for one hour before being injected. The reactor wascharged with 900 mL of dry toluene and pressurized with 300 psig ofethylene, which was fed as needed during polymerization to maintain thepressure. Polyethylene yield: 55.0 g. M.P.(onset of first melt): 131.8°C. The melt flow index (MFI) was too low to be measured. The molecularweight (via GPC) was as follows: Mw=579,652, Mn-243,129, Mw/Mn=2.38.

[0219] Examples 15-19 illustrate the preparation, isolation, and storagestability of the isolated catalyst compounds at ambient roomtemperatures. In these Examples, the stability of the catalyst wasmonitored by UV-Vis spectroscopy. In this method, it is assumed that theabsorbance of the bathochromically shifted metallocenium ion correlateswith the catalyst activity; i.e., the higher the absorbance, the morecatalytically active the metallocene. This correlation has been verifiedby Deffieux's research group in three recently published papers: D.Coevoet et al. Macromol. Chem. Phys., 1998, 199, 1451-1457; D. Coevoetet al. Macromol. Chem. Phys., 1998, 199, 1459-1464; and J. N. Pedeutouret al. Macromol. Chem. Phys., 1999,199, 1215-1221.

[0220] In Example 10 above, it is shown that the starting metallocenehaving an LMCT band at 394 nm diminishes upon activation by HO-IBAO. Thedisappearance is accompanied by the growth of a broad absorption bandextended just beyond 700 nm. In Examples 15 et seq., use is made of theabsorbance at 600 nm for the purpose of monitoring stability. All Uv-Vissamples have a same [Zr] concentration of 0.346 MM (2 umol Zr in 5 g oftoluene) in toluene.

EXAMPLE 15 Polymerization Using rac-ethylene bis(1-indenyl)zirconiumDimethyl Pre-catalyst

[0221] A 15 ml high pressure mini-reactor was placed in a drybox andequipped with a plastic anchor stirrer rotating at about 500 rpm.Hydroxyisobutylaluminoxane previously was made by hydrolyzing TIBA withone equivalent of water, and at the time of use in this polymerizationcontained about 4-5 OH groups per 100 Aluminum atoms. The metallocene,rac-ethylene bis(1-indenyl)zirconium dimethyl, was slurried in hexane inthe mini-reactor at ambient temperature, and thehydroxyisobutylaluminoxane was added thereto. The metallocene quicklydissolved to give a deep red solution. The Al/Zr molar ratio was 30:1.The mini-reactor was then charged with aportion of the catalystcomposition (0.2 micromoles Zr) and a 3 wt % TIBA solution in hexane(about 1 micromole Al). The reactor was then sealed and 6 ml of liquidpropylene was pressed into the reactor via a syringe pump to start thepolymerization. The temperature was quickly brought to 65° C. withinfour to six minutes. The polymerization was allowed for another 10minutes at 65° C., during which time all propylene was consumed. Afterdrying, 3.5 g of polypropylene was collected. The C13-nmr of the polymershowed mmmm % equal to 84.5% and isotacticity index of 94.1%.

EXAMPLE 16 Stability of MET-A +HO-IBAO as an Isolated Product(Al/Zr=200)

[0222] To a suspension of dimethylsilylbis(2-methylindenyl)zirconiumdimethyl (MET-A) (30 mg, 68 μmol) in 10 mL hexanewas added a solutionofhydroxyisobutylaluminoxane (HO-IBAO) (13.2 g, 20 mmol Al) withstirring. Prior to the addition, the solution and the suspension wereboth cooled to −10° C. and after mixing, the resulting mixture wasallowed to return to room temperature. The metallocene graduallydissolved to give a deep red-brown solution. After 45 minutes ofstirring, the solution was stripped of volatiles under vacuum toinitially give a foamy residue which was broken up by a spatula. Another2 hours of pumping yielded a completely dry brown powder which weighed1.4g. The brown solid was stored in a drybox at room temperature, andwas periodically sampled for stability determinations. Each sample wasredissolved in toluene, and the stability of the product was monitoredby UV-Vis at 600 nm by measuring the metallocenium concentration of therespective redissolved samples. Samples were taken right after theisolated product had been dried, and after the isolated product had beenstored for 6 days, 15 days, and 39 days. The results, summarized inTable 1, show that the metallocenium concentration stayed constantthroughout at least a 39-day period. After one month of storage, thesolid product was shown by a micro calorimetric test system to be highlyactive in ethylene polymerization (50° C./50 psi in toluene). TABLE 1Change of UV-Vis Absorbance At 600 nm With Time Storage Time Product ofExample 16 Right after drying 0.183 6 Days 0.181 15 Days 0.187 39 Days0.182

EXAMPLE 17 Stability of MET-A +HO-IBAO Product Dissolved in Toluene

[0223] A catalyst solution of Met-A and HO-IBAO with an Al/Zr molarratio of 100, was prepared. This solution was divided into twosolutions, sample A and B, whose UV-Vis spectra upon storage over timewere recorded. Sample A was stored at ambient temperature in a drybox atall times. Sample B was stored at ambient temperature for the first 4.5hours, and after that was stored at −10° C. except during the spectraacquisition which is done at room temperature. The results aresummarized in Table 2, in which the values marked with an asterisk arevalues of samples taken from the product while the product was beingstored at −10° C. TABLE 2 Change of UV-Vis Absorbance At 600 nm WithTime Storage Time Sample A Sample B 2 Hours 0.149 0.153 4.5 Hours 0.1350.127 28 Hours 0.101 0.126* 5 Days 0.081 0.124* 12 Days 0.064 0.121*

[0224] The results in Table 2 clearly show that the catalyst is unstablein solution at ambient room temperature but is rather stable in solutionat −10° C.

EXAMPLE 18 Stability of MET-A +HO-IBAO as an Isolated Product (Al/Zr=50)

[0225] To a solution of HO-IBAO inhexane (6.78 g, 10.2 mmol Al) and 6.1g toluene was added solid MET-A (88 mg, 204 umol) while the solution wascold. As a consequence of a lower Al/Zr ratio used in this Example,toluene was needed to dissolve the metallocene. After 23 minutes ofstirring at room temperature, the resulting dark brown solution wasstripped of volatiles in vacuo to give a foamy residue which was brokenup by a spatula. After a further 4 hours of pumping, 1.1 g of a brownpowder was isolated. The UV-Vis absorbances of this product at 600 nmwere 0.116 and 0.120 for solids sampled right after drying and after 6days of storage at ambient temperature, respectively.

EXAMPLE 19 Stability of MET-A +HO-IBAO as an Isolated Product(Al/Zr=300)

[0226] The procedure of Example 17 was followed except that MET-A (100μmol) and HO-IBAO in hexane (30 mmol Al) were used and no additionalhexane was used. After drying, 3.2 g of a purple-brown solid wasisolated. The results of the UV-Vis monitoring are summarized in Table3. TABLE 3 Change of UV-Vis Absorbance At 600 nm With Time Storage TimeProduct of Example 19 Right after drying 0.205 11 Days 0.178 24 Days0.177

EXAMPLE 20 Stability of MET-A +HO-IBAO as an Isolated Product (Al/Zr=60)

[0227] The HO-IBAO used in this Example is more freshly prepared thanthat in the Example 18. As a consequence, no toluene was needed todissolve the metallocene. Thus, the procedure in the Example 17 wasfollowed except that MET-A (200 umol), HO-IBAO in hexane (12 mmol Al),and an additional 4 g of hexane were used. After drying, 1.35 g of apurple-brown solid were isolated. The results of the UV-Vis monitoringare summarized in Table 4. TABLE 4 Change of UV-Vis Absorbance At 600 nmWith Time Storage Time Product of Example 20 Right after drying 0.121 6Days 0.122 20 Days 0.132

[0228] For the following Examples 21-44, it will be noted that thehydroxyaluminoxane/silica materials were more difficult to characterizeusing DRIFTS. Without desiring to be bound by theory, it is believedthat the difficulties arise from the many types of OH groups, externalor internal, existing in silica which overlap with the OH groups ofhydroxyaluminoxane in the 3600-3800 cm-1 region in IR (the internal OHgroups of silica may be particularly troublesome since they cannot beeliminated by calcination or AlR₃ treatment). To overcome this problem,deuterated DO-IBAO was prepared by using D₂O in the hydrolysis of TIBAand the deuterated DO-IBAO was compared spectroscopically with HO-IBAOof identical composition. FIG. 8 shows the subtraction result of theDRIFTS spectra of the two materials; one bears OH (negative adsorptions,3600-3800 cm-1) and another OD (positive adsorptions, 2600-2800 cm-1).The subtracted spectrum eliminates the adsorption components from thesilica's OH groups and, thus, unambiguously proves the existence of theOH groups from IBAO.

[0229] Another problem encountered in characterizing thehydroxyaluminoxane/silica is the quantitative analysis of this class ofmaterial. Again without desiring to be bound to theory, it is believedthat the DRIFTS spectroscopy is inadequate in this respect because theheight of the adsorption (see FIG. 8) is somewhat sensitive to thematerial's surface area and its packing and flatness in the sampleholder. Consequently, a chemical method was designed for quantifying theOH groups. Again, the deuterated DO-IBAO proved to be useful. Treatmentof DO-IBAO/silica with an excess of benzylmagnesium chloride solutiongenerated mono-deuterated toluene (DCH₂Ph) which was then collected byvacuum distillation. FIG. 9 shows the H¹-nmr spectrum of such adistillate in CDCl₃. The great virtue of this method is believed to bethat the methyl group resonances of DCH₂Ph and toluene are sufficientlyresolved to allow easy integration. Toluene was present in thedistillate because the commercial benzyl Grignard reagent contained sometoluene and the surface OH of silica can also contribute to tolueneformation. With this method in hand, we were then able to study thestability of the OH groups on HO-IBAO/silica. Two samples ofDO-IBAO/silica were prepared for this study: Sample (1)—silica notreatment; IBAO with a hydrolysis ratio of 1.04, and Sample (2)—silicatreated with excess TEA; IBAO with a hydrolysis ratio of 1.16. Theloadings of the IBAO on silica were about 35% by weight for sample (1)and about 24% by weight for sample (2).

[0230]FIG. 8 shows the OD decay of the two samples and their comparisonwith that of the soluble HO-IBAO (hydrolysis ratio 1.0). The sample (1),in which silica was not treated with AlR3, has a decay profile that isquite similar to that of the soluble HO-IBAO except that its lifetime islonger at room temperature than that of soluble HO-IBAO at −10° C. Thesample (2) was hydrolyzed more, thereby having more than 10 OH groupsper 100 aluminums at the start. Strikingly, it has an OH decay profilethat is very different from the other two. It features an almost lineardecay and is a lot steeper, undoubtedly a result of its silicapre-treatment with TEA.

EXAMPLES 21-27 Synthesis of HO-IBAO/Silica

[0231] Preparations of all HO-IBAO/silica are summarized in Table 5.Silica, obtained from Crosfield (ES-70), was calcined either at 200° C.or 600° C. for 4 hours. Some of them were pre-treated with AlR₃ (diluteTEA or TIBA in hexane) at room temperature for one hour followed byfiltration.

[0232] A typical procedure is as follows (Example 27): To a freshlyprepared hydroxy IBAO solution inhexane (61.4 g, 87 mmol Al, hydrolysisratio=l.04) was added silica (15.0 g, calcined at 600° C., no AlR₃treatment) and stirred with a magnetic stir bar for 2 hours. After that,the slurry was allowed to settle. At this point, if there is anappreciable amount of supernatant, it may be separated from silica bydecant (see Table 5). In this example, there was no decant. Instead, theslurry was stripped of volatiles under vacuo, which was done slowly toprevent loss of fine silica particles. After drying, 23.0 g ofHO-IBAO/silica was collected, a 34.8% of IBAO loading. The ICP analysisof this solid showed 10.0 wt % Al. For deuterium-labeled DO-IBAO/silicasamples (Example 28), this procedure was followed except that D₂Oinstead of H₂O was used. TABLE 5 Summary of HO-IBAO/silica preparationSilica IBAO calcine wt % Hydrolysis reaction loading wt % Al Ex. (° C.)AlR₃ Al ratio time (hr) decant (wt %) (total) 21 600 TEA 3.0 1.18 16 no23.8 10.1 22 200 TIBA 3.2 1.18 16 yes 22.1 9.86 23 600 no 0 1.18 16 no23.7 7.53 24 600 no 0 1.18 4 yes 33.2 10.0 25 600 TEA 3.3 1.18 18 no24.5 10.2 26 600 TEA 3.3 1.18 4 yes 20.5 8.9 27 600 no 0 1.04 2 no 34.810.0

EXAMPLE 28 Quantifying the OD Groups in DO-IBAO/Silica

[0233] For quantitative purposes, because silica was used as the carriermaterial, the use of a deuterium-labeled DO-hydroxyaluminoxane/silica,and in this case DO-IBAO/silica, was preferred. Samples (1) and (2) werestored at room temperature in a drybox and were sampled periodically forquantitative analysis (see FIG. 10). A typical procedure was as follows.To the sample (1) DO-IBAO/silica (3.0 g, 11.1 mmol Al) in around-bottomed flask was added a 2.0M solution of benzylmagnisiumchloride in THF (4.80 g). Additional THF (4.5 g) was added to aidstirring. The slurry was stirred for one hour at room temperature. Afterthat all volatiles were carefully vacuum-distilled off the solid residueat temperatures finally reaching 55° C. and collected in a liquidnitrogen trap. The amount of DCH₂Ph in the volatiles collected wasdetermined by H¹-nmr in CDCl₃. From that, the hydroxyl content wasdetermined to be 7.5 OD per 100 aluminums.

EXAMPLES 29-35 Preparation of Catalyst fromrac-dimethylsilylbis(2-methylindenyl)zirconium Dimethyl Activated byHO-IBAO/Silica

[0234] The synthesis of HO-IBAO activated silica-supported catalysts(see Table 6 for summary) is exemplified as follows (Example 35): To aslurry of HO-IBAO/silica (1.45 g) in hexane (12 ml) was addedparticulate rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl (86mg) and the mixture was allowed to stir at room temperature. After 75minutes, the resulting deep brown slurry was filtered, solids washedseveral times with hexane until the filtrate was colorless, and suctiondried for 10 minutes to give a yellowish brown solid, weighing 1.42 g.The ICP analysis of this solid showed 8.8 wt % Al and 1.0 wt % Zr, whichcorresponds to a Al/Zr molar ratio of 29. TABLE 6 Properties ofrac-Dimethylsilylbis(2-methylindenyl)zirconium Dimethyl-HO-IBAG-SilicaCatalysts Catalyst Example IBAO/silica wt % Al wt % Zr Al/Zr 29 21 10.20.46 53 30 22 8.1 0.54 51 31 23 8.4 0.43 41 32 24 10.1 1.3 26 33 25 8.70.46 64 34 26 7.6 0.40 65 35 27 8.8 1.0 29

EXAMPLES 36-42

[0235] For each catalyst synthesized in Examples 29-35, polymerizationof propylene was carried out in a 4-liter reactor charged with 2200 mlof liquid propylene. At 65° C. with vigorous stirring, 1.0 ml of 5% TIBA(as scavenger) was injected into the reactor first, which was quicklyfollowed by another injection of the catalyst (110 mg slurried in 2 mlof dry hexane) to initiate polymerization. After one hour of reaction,the unreacted propylene was quickly vented. The results are summarizedin Table 7. No reactor fouling was seen in any of the polymerizations.TABLE 7 Summary of Propylene Polymerization Results Polymer CatalystBulk Catalyst Polymer Activity Density Melting Point MFI GPC Ex.Catalyst weight (mg) Yield (g) (g/g/h) (g/ml) (onset/peak) (° C.) (230°C./5 kg) Mw Mn Mw/Mn 36 29 154 396 2568 0.37 144.58/150.08 35.89 — — —37 30 206 15 73 0.28 — — — — — 38 31 165 367 2218 0.40 143.52/149.3939.73 253000 147000 1.72 39 32 164 247 1506 0.28 143.25/149.09 31.93300000 180000 1.67 40 33 160 170 1059 0.21 142.28/148.85 34.54 261000157000 1.66 41 34 161 39 243 0.15 — — — — — 42 35 41 185 4512 0.38143.01/148.85 28.47 267000 155000 1.72

EXAMPLE 43 Preparation of Catalyst from rac-ethylenebis(tetrahydroindenyl)zirconium Dimethyl Activated by HO-IBAO/Silica

[0236] The synthesis of this silica-supported catalyst was as describedin examples 29-35 except that HO-IBAO/silica (1.98 g), hexane (18 ml),and rac-ethylene bis(tetrahydroindenyl)zirconium dimethyl (160 mg) wereused and the mixture was allowed to stir at room temperature for 85minutes. The product was a pink solid, weighing 1.97 g. The ICP analysisof this solid showed 8.8 wt % Al and 1.3 wt % Zr, which corresponds to aAl/Zr molar ratio of 23.

EXAMPLE 44 Ethylene Polymerization

[0237] The polymerization was cairied out in a 4-liter reactor which wascharged with 1000 ml of isobutane and 40 ml hexene (pushed in by another500 ml of isobutene), sequentially. After stabilizing at 80° C., thereactor was pressurized with ethylene from 145 psig to 345 psig. Withvigorous stirring (600 rpm), 2.0 ml of 5% TIBA (as scavenger) wasinjected into the reactor first, which was quickly followed by aninjection of the catalyst from Example 43 (77.7 mg slurried in 3 ml ofdry hexane) to initiate polymerization. The reactor pressure wasmaintained at 315 psig by adding more make up ethylene. After one hourof reaction, unreacted ethylene and isobutane were quickly vented. Thepolyethylene fluff after drying weighed 198 g. No reactor fouling wasseen. Polymer properties: bulk density: 0.31 g/cc; M.P.: 109.17/121.09°C. (onset of second melt/peak). Melt flow index (190° C./5 kg) was toolow to measure (<0.1 g/10 min). Molecular weight via GPC was as follows:Mw=640,000, Mn=296,000, Mw/Mn=2.16.

[0238] While this invention has been specifically illustrated byreactions between a metallocene and a hydroxyaluminoxane, it is to beunderstood that other suitable organometallic reactants having anappropriate leaving group can be employed. For example it iscontemplated that the organometallic complexes described in thefollowing publications will form ionic compounds of this invention,provided that at least one of the halogen atoms bonded to the d-block orf-block metal atom is replaced by a suitable leaving group such as amethyl, benzyl, or trimethylsilylmethyl group:

[0239] Small, B. L.; Brookhart, M.; Bennett, A, M. A. J. Am. Chem. Soc.1998, 120, 4049.

[0240] Small, B. L.; Brookhart, M. J. Am. Chem. Soc. 1998,120 7143.

[0241] Johnson, L. K.; Killian, C. M.; Brookhart, M. J. Am. Chem. Soc.1995, 117, 6414.

[0242] Killian, C. M.; Johnson, L. K.; Brookhart, M. Organometallics1997, 16, 2005.

[0243] Killian, C. M.; Tempel, D. J.; Johnson, L. K.; Brookhart, M. J.Am. Chem. Soc. 1996, 118, 11664.

[0244] Johnson, L. K.; Mecking, S.; Brookhart, M. J. Am. Chem. Soc.1996, 118, 267.

[0245] It will now be appreciated that this invention is susceptible toconsideration variation in its practice, as the invention providesnumerous advantages and features. Some of these advantages and featurescan be expressed in terms of the various embodiments of the inventionitself. The following comprises non-limiting examples of suchembodiments:

[0246] A1. A composition in the form of one or more individual solids,which composition is formed from components comprised of (i) ahydroxyaluminoxane and (ii) a carrier material compatible with saidhydroxyaluminoxane and in the form of one or more individual solids,said composition having a reduced OH-decay rate relative to the OH-decayrate of (i).

[0247] A2. A composition according to A1 wherein (i) is supported on(ii).

[0248] A3. A composition according to A2 wherein (ii) consistsessentially of a particulate inorganic catalyst support material.

[0249] A4. A composition according to A3 wherein said inorganic catalystsupport material is comprised of anhydrous or substantially anhydrousparticles of silica, silica-alumina, or alumina.

[0250] A5. A composition according to A3 wherein said inorganic catalystsupport material consists essentially of a particulate porous calcinedsilica.

[0251] A6. A composition according to A3 wherein said inorganic catalystsupport material consists essentially of a particulate porous silicapretreated with an aluminum alkyl.

[0252] A7. A composition according to any of A1, A2, A3, A4, A5, or A6wherein said hydroxyaluminoxane of (i) has less than 25 OH groups per100 aluminum atoms.

[0253] A8. A composition according to any of A1, A2, A3, A4, A5, or A6wherein said hydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.

[0254] A9. A composition according to any of A1, A2, A3, A4, A5, or A6wherein said composition is substantially insoluble in an inert organicsolvent.

[0255] A10. A composition according to A9 wherein saidhydroxyaluminoxane of (i) has less than 25 OH groups per 100 aluminumatoms.

[0256] A11. A composition according to A9 wherein saidhydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.

[0257] A12. A composition according to any of A1, A2, A3, A4, A5, or A6wherein the OH-decay rate of said composition is reduced relative to theOH-decay rate of (i) by a factor of at least 5.

[0258] A13. A composition according to A12 wherein saidhydroxyaluminoxane of (i) has less than 25 OH groups per 100 aluminumatoms.

[0259] A14. A composition according to A12 wherein saidhydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.

[0260] A15. A composition according to A12 wherein said composition issubstantially insoluble in an inert organic solvent.

[0261] B1. A composition comprising a hydroxyaluminoxane supported on asolid support.

[0262] B2. A composition according to B1, wherein said composition ischaracterized by having an OH-decay rate which is reduced as compared tothe OH-decay rate of the hydroxyaluminoxane in a liquid or solidunsupported form.

[0263] B3. A composition according to B2 wherein the OH-decay rate ofsaid composition is reduced, as compared to that of saidhydroxyaluminoxane in unsupported form, by a factor of at least 5.

[0264] B4. A composition according to any of B1, B2, or B3 wherein saidhydroxyaluminoxane has less than 25 hydroxyl groups per 100 aluminumatoms.

[0265] B5. A composition according to any of B1, B2, or B3 wherein saidhydroxyaluminoxane consists essentially of hydroxyisobutylaluminoxane.

[0266] B6. A composition according to any of B1, B2, or B3 wherein saidsolid support is a particulate inorganic catalyst support material.

[0267] B7. A composition according to B6 wherein said inorganic catalystsupport material is comprised of anhydrous or substantially anhydrousparticles of silica, silica-alumina, or alumina.

[0268] B8. A composition according to B6 wherein said inorganic catalystsupport material consists essentially of a particulate porous silicapretreated with an aluminum alkyl.

[0269] C1. A process comprising converting a hydroxyaluminoxane into acomposition in the form of one or more individual solids by bringingtogether (i) a hydroxyaluminoxane and (ii) a carrier material compatiblewith said hydroxyaluminoxane and in the form of one or more individualsolids, whereby the rate of OH-decay for said composition is reducedrelative to the rate of OH-decay of (i).

[0270] C2. A process according to C1 wherein (i) is converted into saidcomposition by supporting (i) on (ii).

[0271] C3. A process according to C2 wherein (ii) consists essentiallyof a particulate inorganic catalyst support material.

[0272] C4. A process according to C3 wherein said inorganic catalystsupport material is comprised of anhydrous or substantially anhydrousparticles of silica, silica-alumina, or alumina.

[0273] C5. A process according to C3 wherein said inorganic catalystsupport material consists essentially of a particulate porous calcinedsilica.

[0274] C6. A process according to C3 wherein said inorganic catalystsupport material consists essentially of a particulate porous silicapretreated with an aluminum alkyl.

[0275] C7. A process according to any of C1, C2, C3, C4, C5, or C6wherein said hydroxyaluminoxane of (i) has less than 25 OH groups per100 aluminum atoms.

[0276] C8. A process according to C7 wherein said hydroxyaluminoxane of(i) consists essentially of hydroxyisobutylaluminoxane.

[0277] C9. A process according to any of C1, C2, C3, C4, C5, or C6wherein the OH-decay rate of said composition is reduced, as compared tothe OH-decay rate of (i), by a factor of at least 5.

[0278] C10. A process according to C9 wherein said hydroxyaluminoxane of(i) has less than 25 OH groups per 100 aluminum atoms.

[0279] C11. A process according to C10 wherein said hydroxyaluminoxaneof (i) consists essentially of hydroxyisobutylaluminoxane.

[0280] C12. A process according to C9, wherein said composition isinsoluble or substantially insoluble in an inert organic solvent.

[0281] D1. A supported activated catalyst composition formed by bringingtogether (A) a composition in the form of one or more individual solids,which composition is formed from components comprised of (i) ahydroxyaluminoxane and (ii) a carrier material compatible with saidhydroxyaluminoxane and in the form of one or more individual solids,said composition of (A) having a reduced OH-decay rate relative to theOH-decay rate of (i); and (B) a d- or f-block metal compound having atleast one leaving group on a metal atom thereof.

[0282] D2. A catalyst composition according to D1 wherein said d- orf-block metal compound is a Group 4 metal.

[0283] D3. A catalyst composition according to D1 wherein said d- orf-block metal compound is a metallocene.

[0284] D4. A catalyst composition according to D3 wherein the d- orf-block metal of said metallocene is at least one Group 4 metal.

[0285] D5. A catalyst composition according to D3 wherein saidmetallocene contains two bridged or unbridgedcyclopentadienyl-moiety-containing groups.

[0286] D6. A catalyst composition according to D5 wherein the Group 4metal of said metallocene is zirconium.

[0287] D7. A catalyst composition according to D5 wherein the Group 4metal of said metallocene is titanium.

[0288] D8. A catalyst composition according to D5 wherein the Group 4metal of said metallocene is hafnium.

[0289] D9. A catalyst composition according to any of D1, D2, D3, D4,D5, D6, D7, or D8 wherein said hydroxyaluminoxane of (i) has less than25 hydroxyl groups per 100 aluminum atoms.

[0290] D10. A catalyst composition according to any of D1, D2, D3, D4,D5, D6, D7, or D8 wherein said hydroxyaluminoxane of (i) consistsessentially of hydroxyisobutylaluminoxane.

[0291] D11. A catalyst composition according to any of D1, D2, D3, D4,D5, D6, D7, or D8 wherein (ii) consists essentially of a particulateinorganic catalyst support material.

[0292] D12. A catalyst composition according to D1 wherein said catalystsupport material is comprised of anhydrous or substantially anhydrousparticles of silica, silica-alumina, or alumina.

[0293] D13. A catalyst composition according to D11 wherein saidinorganic catalyst support material consists essentially of aparticulate porous calcined silica.

[0294] D14. A catalyst composition according to D11 wherein saidinorganic catalyst support material consists essentially of aparticulate porous silica pretreated with an aluminum alkyl.

[0295] D15. A catalyst composition according to any of D1, D2, D3, D4,D5, D6, D7, or D8 wherein said composition in a dry or substantially drystate is able to be maintained at a temperature in the range of about 10to about 60° C. for a period of at least 48 hours without losing fiftypercent (50%) or more of its catalytic activity.

[0296] E1. A process of preparing a supported activated catalyst, whichprocess comprises bringing together (A) a composition in the form of oneor more individual solids formed by bringing together (i) ahydroxyaluminoxane and (ii) a carrier material compatible with saidhydroxyaluminoxane and in the form of one or more individual solids,whereby the rate of OH-decay for said composition is reduced relative tothe rate of OH-decay of (i); and (B) a d- or f-block metal compoundhaving at least one leaving group on a metal atom thereof.

[0297] E2. A process according to E1 wherein (A) and (B) are broughttogether in an inert diluent.

[0298] E3. A process according to E1 wherein (A) and (B) are broughttogether in the absence of an inert diluent.

[0299] E4. A process according to E1 wherein said hydroxyaluminoxane of(i) consists essentially of hydroxyisobutylaluminoxane.

[0300] E5. A process according to E1 wherein said hydroxyaluminoxane of(i) has less than 25 hydroxyl groups per 100 aluminum atoms.

[0301] E6. A process according to E1 wherein (ii) is a particulateinorganic catalyst support material.

[0302] E7. A process according to E6 wherein said inorganic catalystsupport material is comprised of anhydrous or substantially anhydrousparticles of silica, silica-alumina, or alumina.

[0303] E8. A process according to E6 wherein said inorganic catalystsupport material consists essentially of a particulate porous calcinedsilica.

[0304] E9. A process according to E6 wherein said inorganic catalystsupport material consists essentially of a particulate porous silicapretreated with an aluminum alkyl.

[0305] E10. A process according to E1 wherein said d- or f-block metalcompound is a metallocene.

[0306] Eb 11. A process according to E10 wherein said at least oneleaving group of said metallocene is a methyl group.

[0307] E12. A process according to E10 wherein said metallocene containstwo bridged or unbridged cyclopentadienyl-moiety-containing groups.

[0308] E13. A process according to E12 wherein the metal of saidmetallocene is a Group 4 metal.

[0309] E14. A process according to E13 wherein said Group 4 metal iszirconium.

[0310] E15. A process according to E13 wherein said Group 4 metal istitanium.

[0311] E16. A process according to E13 wherein said Group 4 metal ishafnium.

[0312] E17. Aprocess according to any of E1, E2, E3, E4, E5, E6, E7, E8,E9, E10, E11, E12, E13, E14, E15, or E16, wherein said supportedactivated catalyst is recovered and maintained at a temperature in therange of about 10 to about 60° C. for a period of at least 48 hourswithout losing fifty percent (50%) or more of its catalytic activity.

[0313] F1. An olefin polymerization process which comprises bringingtogether in a polymerization reactor or reaction zone (1) at least onepolymerizable olefin and (2) a supported activated catalyst compositionwhich is in accordance with any of C1, C2, C3, C4, C5, C6, C7, or C8.

[0314] F2. An olefin polymerization process according to F1 wherein thepolymerization process is conducted as a gas-phase polymerizationprocess.

[0315] F3. An olefin polymerization process according to F1 wherein thepolymerization process is conducted in a liquid phase diluent.

[0316] F4. An olefin polymerization process according to F1 wherein thepolymerization process is conducted as a fluidized bed process.

[0317] F5. An olefin polymerization process according to F1 wherein saidhydroxyaluminoxane of (i) has less than 25 hydroxyl groups per 100aluminum atoms.

[0318] F6. An olefin polymerization process according to F5 wherein thepolymerization process is conducted as a gas-phase polymerizationprocess.

[0319] F7. An olefin polymerization process according to F5 wherein thepolymerization process is conducted in a liquid phase diluent.

[0320] F8. An olefin polymerization process according to F5 wherein thepolymerization process is conducted as a fluidized bed process.

[0321] F9. An olefin polymerization process according to F1 wherein saidhydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.

[0322] F10. An olefin polymerization process according to F1 wherein(ii) consists essentially of a particulate inorganic catalyst supportmaterial.

[0323] F11. An olefin polymerization process according to F10 whereinsaid catalyst support material is comprised of anhydrous orsubstantially anhydrous particles of silica, silica-alumina, or alumina.

[0324] F12. An olefin polymerization process according to F10 whereinsaid inorganic catalyst support material consists essentially of aparticulate porous calcined silica.

[0325] F13. An olefin polymerization process according to F10 whereinsaid inorganic catalyst support material consists essentially of aparticulate porous silica pretreated with an aluminum alkyl.

[0326] F14. An olefin polymerization process according to F10 whereinthe polymerization process is conducted as a gas-phase polymerizationprocess.

[0327] F15. An olefin polymerization process according to F10 whereinthe polymerization process is conducted in a liquid phase diluent.

[0328] F16. An olefin polymerization process according to F10 whereinthe polymerization process is conducted as a fluidized bed process.

[0329] G1. A catalyst composition formed by bringing together (A) ahydroxyaluminoxane and (B) rac-ethylene bis(1-indenyl)zirconiumdimethyl.

[0330] G2. A catalyst composition according to G1 wherein (A) and (B)are brought together in an inert diluent.

[0331] G3. A catalyst composition according to G1 wherein (A) and (B)are brought together in the absence of an inert diluent.

[0332] G4. A catalyst composition according to any of G1, G2, or G3wherein said hydroxyaluminoxane of (A) has less than 25 hydroxyl groupsper 100 aluminum atoms.

[0333] G5. A catalyst composition according to G4 wherein saidcomposition in a dry state is able to be maintained at a temperature inthe range of about 10 to about 60° C. for a period of at least 48 hourswithout losing fifty percent (50%) or more of its catalytic activity.

[0334] G6. A catalyst composition according to any of G1, G2, or G3wherein said hydroxyaluminoxane of (A) consists essentially ofhydroxyisobutylaluminoxane.

[0335] G7. A catalyst composition according to G6 wherein saidcomposition in a dry state is able to be maintained at a temperature inthe range of about 10 to about 60° C. for a period of at least 48 hourswithout losing fifty percent (50%) or more of its catalytic activity.

[0336] G8. A catalyst composition according to any of G1, G2, or G3wherein said hydroxyaluminoxane of (A) is supported on a particulateinorganic catalyst support material.

[0337] G9. A catalyst composition according to G8 wherein said inorganiccatalyst support material is comprised of anhydrous or substantiallyanhydrous particles of silica, silica-alumina, or alumina.

[0338] G10. A catalyst composition according to G8 wherein saidinorganic catalyst support material consists essentially of aparticulate porous silica pretreated with an aluminum alkyl.

[0339] G11. A catalyst composition according to G8 wherein saidcomposition in a dry state is able to be maintained at a temperature inthe range of about 10 to about 60° C. for a period of at least 48 hourswithout losing fifty percent (50%) or more of its catalytic activity.

[0340] H1. A process for the production of a supportedhydroxyaluminoxane which comprises bringing together (i) an aluminumalkyl in an inert solvent, (ii) a water source, and (iii) a carriermaterial, under hydroxyaluminoxane-forming reaction conditions.

[0341] H2. A process according to H1 wherein said aluminum alkyl is atrialkylaluminum.

[0342] H3. A process according to Hi wherein said water source consistsessentially of free water.

[0343] H4. A process according to H1 wherein said water source consistsessentially of a hydrated inorganic salt or un-dehydrated silica.

[0344] H5. A process according to H1 wherein said carrier material is asolid support.

[0345] H6. A process according to H5 wherein said solid support is aparticulate inorganic catalyst support material.

[0346] H7. A process according to H6 wherein said inorganic catalystsupport material is comprised of anhydrous or substantially anhydrousparticles of silica, silica-alumina, or alumina.

[0347] H8. A process according to H6 wherein said inorganic catalystsupport material consists essentially of a particulate porous calcinedsilica.

[0348] H9. A process according to H6 wherein said inorganic catalystsupport material consists essentially of a particulate porous silicapretreated with an aluminum alkyl.

[0349] J1. A method of forming an olefin polymerization catalyst, whichmethod comprises feeding into a vessel (A) a hydroxyaluminoxane and (B)a d- or f-block metal compound in proportions such that an active olefinpolymerization catalyst is formed.

[0350] J2. A method according to J1 wherein the hydroxyaluminoxane isfed in the form of a solution formed from the hydroxyaluminoxane in aninert solvent or in a liquid polymerizable olefinic monomer, or both.

[0351] J3. A method according to J1 wherein the hydroxyaluminoxane isfed in the form of a slurry formed from the hydroxyaluminoxane in aninert diluent or in a liquid polymerizable olefinic monomer.

[0352] J4. A method according to J1 wherein the hydroxyaluminoxane isfed in the form of unsupported solid particles.

[0353] J5. A method according to J1 wherein the hydroxyaluminoxane isfed in the form of one or more solids on a carrier material.

[0354] J6. A method according to J1 wherein the hydroxyaluminoxane isfed in the form of (i) a solution formed from the hydroxyaluminoxane inan inert solvent or in a liquid polymerizable olefinic monomer, or both;(ii) a slurry formed from the hydroxyaluminoxane in an inert diluent orin a liquid polymerizable olefinic monomer; (iii) unsupported solidparticles; or (iv) one or more solids on a carrier material; or (v) anycombination of two or more of (i), (ii), (iii), and (iv).

[0355] J7. A method according to any of J1, J2, J3, J4, J5, or J6wherein the d- or f-block metal compound is fed in the form of undilutedsolids or liquid.

[0356] J8. Amethod according to any of J1, J2, J3, J4, J5, orJ6 whereinthe d- or f-block metal compound is fed in the form of a solution orslurry of the d- or f-block metal compound in an inert solvent ordiluent, or in a liquid polymerizable olefinic monomer, or in a mixtureof any of these.

[0357] K1. In a process for the catalytic polymerization of at least oneolefin in a reaction vessel or reaction zone, the improvement whichcomprises introducing into the reaction vessel or reaction zone catalystcomponents comprising (A) a hydroxyaluminoxane and (B) a d- or f-blockmetal compound, in proportions such that said at least one olefin ispolymerized.

[0358] K2. The improvement according to K1 wherein thehydroxyaluminoxane is introduced in the form of a solution formed fromthe hydroxyaluminoxane in an inert solvent or in a liquid form of saidat least one olefin, or both.

[0359] K3. The improvement according to K1 wherein thehydroxyaluminoxane is introduced in the form of a slurry formed from thehydroxyaluminoxane in an inert diluent or in a liquid form of said atleast one olefin.

[0360] K4. The improvement according to K1 wherein thehydroxyaluminoxane is introduced in the form of unsupported solidparticles.

[0361] K5. The improvement according to K1 wherein thehydroxyaluminoxane is introduced in the form of one or more solids on acarrier material.

[0362] K6. The improvement according to K5 wherein the one or moresolids on the carrier material are in an inert viscous liquid.

[0363] K7. The improvement according to K1 wherein thehydroxyaluminoxane is introduced in the form of (i) a solution formedfrom the hydroxyaluminoxane in an inert solvent or in a liquid form ofsaid at least one olefin, or both; (ii) a slurry formed from thehydroxyaluminoxane in an inert diluent or in a liquid form of said atleast one olefin; (iii) unsupported solid particles; or (iv) one or moresolids on a carrier material; or (v) any combination of two or more of(i), (ii), (iii), and (iv).

[0364] K8. The improvement according to any of K1, K2, K3, K4, K5, K6,or K7 wherein the d- or f-block metal compound is introduced in the formof undiluted solids or liquid.

[0365] K9. The improvement according to any of K1, K2, K3, K4, K5, K6,or K7 wherein the d- or f-block metal compound is introduced in the formof a solution or slurry of the d- or f-block metal compound in an inertsolvent or diluent, or in a liquid form of said at least one olefin, orin a mixture of any of these.

[0366] The materials referred to by chemical name or formula anywhere inthe specification or claims hereof are identified as ingredients to bebrought together in connection with performing a desired operation or informing a mixture to be used in conducting a desired operation.Accordingly, even though the claims hereinafter may refer to substancesin the present tense (“comprises”, “is”, etc.), the reference is to thesubstance, as it existed at the time just before it was first contacted,blended or mixed with one or more other substances in accordance withthe present disclosure. The fact that a substance may lose its originalidentity through a chemical reaction, complex formation, solvation,ionization, or other transformation during the course of contacting,blending or mixing operations, if done in accordance with the disclosurehereof and with the use of ordinary skill of a chemist and common sense,is within the purview and scope of this invention.

[0367] Each and every patent or other publication referred to in anyportion of this specification is incorporated in full into thisdisclosure by reference, as if fully set forth herein.

[0368] The foregoing description is not intended to limit, and shouldnot be construed as limiting, the invention to the particularexemplifications presented hereinabove. Rather, what is intended to becovered is as set forth in the ensuing claims and the equivalentsthereof permitted as a matter of law.

That which is claimed is:
 1. A composition in the form of one or moreindividual solids, which composition is formed from components comprisedof (i) a hydroxyaluminoxane and (ii) a carrier material compatible withsaid hydroxyaluminoxane and in the form of one or more individualsolids.
 2. A composition according to claim 1 wherein (i) is supportedon (ii).
 3. A composition according to claim 2 wherein (ii) consistsessentially of a particulate inorganic catalyst support material.
 4. Acomposition according to claim 3 wherein said inorganic catalyst supportmaterial is comprised of anhydrous or substantially anhydrous particlesof silica, silica-alumina, or alumina.
 5. A composition according toclaim 3 wherein said inorganic catalyst support material consistsessentially of a particulate porous calcined silica or a particulateporous silica pretreated with an aluminum alkyl.
 6. A compositionaccording to any of claims 1, 3, or 5 wherein said hydroxyaluminoxane of(i) has less than 25 OH groups per 100 aluminum atoms.
 7. A compositionaccording to any of claims 1, 3, or 5 wherein said hydroxyaluminoxane of(i) consists essentially of hydroxyisobutylaluminoxane.
 8. A compositionaccording to any of claims 2, 3, or 5 wherein the OH-decay rate of saidcomposition is reduced relative to the OH-decay rate of (i) by a factorof at least 5, and wherein said hydroxyaluminoxane of (i) has less than25 OH groups per 100 aluminum atoms.
 9. A composition according to claim8 wherein said hydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.
 10. A composition comprising ahydroxyaluminoxane supported on a solid support.
 11. A compositionaccording to claim 10, wherein said composition is characterized byhaving an OH-decay rate which is reduced as compared to the OH-decayrate of the hydroxyaluminoxane in a liquid or solid unsupported form.12. A composition according to claim 11 wherein said OH-decay rate ofsaid composition is reduced, as compared to that of saidhydroxyaluminoxane in a liquid or solid unsupported form, by a factor ofat least
 5. 13. A composition according to any of claims 10, 11, or 12wherein said hydroxyaluminoxane has less than 25 hydroxyl groups per 100aluminum atoms.
 14. A composition according to any of claims 10, 11, or12 wherein said hydroxyaluminoxane consists essentially ofhydroxyisobutylaluminoxane.
 15. A composition according to any of claims10, 11, or 12 wherein said solid support is a particulate inorganiccatalyst support material.
 16. A composition according to claim 10wherein said solid support consists essentially of a particulate poroussilica pretreated with an aluminum alkyl.
 17. A process comprisingconverting a hydroxyaluminoxane into a composition in the form of one ormore individual solids by bringing together (i) a hydroxyaluminoxane and(ii) a carrier material compatible with said hydroxyaluminoxane and inthe form of one or more individual solids, whereby the rate of OH-decayfor said composition is reduced relative to the rate of OH-decay of (i).18. A process according to claim 17 wherein (ii) consists essentially ofa particulate inorganic catalyst support material.
 19. A processaccording to claim 18 wherein said support material is comprised ofanhydrous or substantially anhydrous particles of silica,silica-alumina, or alumina.
 20. A process according to claim 18 whereinsaid support material consists essentially of a particulate porouscalcined silica or a particulate porous silica pretreated with analuminum alkyl.
 21. A process according to any of claims 17, 18 or 20wherein said hydroxyaluminoxane of (i) has less than 25 OH groups per100 aluminum atoms.
 22. A process according to claim 17 wherein saidhydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.
 23. A supported activated catalystcomposition formed by bringing together (A) a composition in the form ofone or more individual solids, which composition is formed fromcomponents comprised of (i) a hydroxyaluminoxane and (ii) a carriermaterial compatible with said hydroxyaluminoxane and in the form of oneor more individual solids; and (B) a d-block or f-block metal compoundhaving at least one leaving group on a d-block or f-block metal atomthereof.
 24. A catalyst composition according to claim 23 wherein thed-block or f-block metal of said d-block or f-block metal compound is aGroup 4 metal.
 25. A catalyst composition according to claim 23 whereinsaid d-block or f-block metal compound is a metallocene.
 26. A catalystcomposition according to claim 25 wherein the d-block or f-block metalof said metallocene is at least one Group 4 metal.
 27. A catalystcomposition according to claim 26 wherein said metallocene contains twobridged or unbridged cyclopentadienyl-moiety-containing groups.
 28. Acatalyst composition according to claim 27 wherein the Group 4 metal ofsaid metallocene is zirconium or hafnium.
 29. A catalyst compositionaccording to any of claims 23, 25, 27, or 28 wherein saidhydroxyaluminoxane of (i) has less than 25 hydroxyl groups per 100aluminum atoms.
 30. A catalyst composition according to any of claims23, 25, 27, or 28 wherein said hydroxyaluminoxane of (i) consistsessentially of hydroxyisobutylaluminoxane.
 31. A catalyst compositionaccording to any of claims 23, 25, 27, or 28 wherein (ii) consistsessentially of a particulate inorganic catalyst support material.
 32. Acatalyst composition according to claim 23 wherein (ii) is comprised ofanhydrous or substantially anhydrous particles of silica,silica-alumina, or alumina.
 33. A catalyst composition according toclaim 31 wherein said support material consists essentially of aparticulate porous calcined silica or a particulate porous silicapretreated with an aluminum alkyl.
 34. A catalyst composition accordingto any of claims 23, 25, 27, or 28 wherein said composition in a dry orsubstantially dry state is able to be maintained at a temperature in therange of about 10 to about 60° C. for a period of at least 48 hourswithout losing fifty percent (50%) or more of its catalytic activity.35. A process of preparing a supported activated catalyst, which processcomprises bringing together (A) a composition in the form of one or moreindividual solids formed by bringing together (i) a hydroxyaluminoxaneand (ii) a carrier material compatible with said hydroxyaluminoxane andin the form of one or more individual solids; and (B) a d-block orf-block metal compound having at least one leaving group on a d-block orf-block metal atom thereof.
 36. A process according to claim 35 wherein(A) and (B) are brought together in the presence of an inert diluentwhich optionally is or includes a solvent or carrier fluid for thehydroxyaluminoxane and/or the d-block or f-block metal compound.
 37. Aprocess according to claim 36 wherein said hydroxyaluminoxane of (i)consists essentially of hydroxyisobutylaluminoxane.
 38. A processaccording to claim 36 wherein said hydroxyaluminoxane of (i) has lessthan 25 hydroxyl groups per 100 aluminum atoms.
 39. A process accordingto claim 36 wherein (ii) is a particulate inorganic catalyst supportmaterial.
 40. A process according to claim 39 wherein said supportmaterial is comprised of anhydrous or substantially anhydrous particlesof silica, silica-alumina, or alumina.
 41. A process according to claim39 wherein said inorganic catalyst support material consists essentiallyof a particulate porous calcined silica or a particulate porous silicapretreated with an aluminum alkyl.
 42. A process according to claim 39wherein said d-block or f-block metal compound is a metallocene.
 43. Aprocess according to claim 42 wherein said at least one leaving group ofsaid metallocene is a methyl group.
 44. A process according to claim 42wherein said metallocene contains two bridged or unbridgedcyclopentadienyl-moiety-containing groups.
 45. A process according toclaim 44 wherein the metal of said metallocene is a Group 4 metal.
 46. Aprocess according to claim 45 wherein said at least one leaving group ofsaid metallocene is a methyl group.
 47. A process according to claim 46wherein said Group 4 metal is zirconium or hafnium.
 48. A processaccording to any of claims 36, 39, 41, 42, 46, or 47, wherein saidsupported activated catalyst is recovered and maintained at atemperature in the range of about 10 to about 60° C. for a period of atleast 48 hours without losing fifty percent (50%) or more of itscatalytic activity.
 49. An olefin polymerization process which comprisesbringing together in a polymerization reactor or reaction zone (1) atleast one polymerizable olefinic monomer and (2) a supported activatedcatalyst composition which is in accordance with any of claims 36, 39,41, 42, 46 or
 47. 50. An olefin polymerization process according toclaim 49 wherein the polymerization process is conducted as a gas-phasepolymerization process.
 51. An olefin polymerization process accordingto claim 49 wherein the polymerization process is conducted in a liquidphase diluent.
 52. An olefin polymerization process according to claim49 wherein the polymerization process is conducted as a fluidized bedprocess.
 53. A catalyst composition formed by bringing together (A) ahydroxyaluminoxane and (B) rac-ethylene bis(1-indenyl)zirconium dimethylin an inert diluent which optionally is or includes a solvent or carrierfluid for the hydroxyaluminoxane and/or the d- or f-block metalcompound.
 54. A catalyst composition according to claim 53 wherein saidhydroxyaluminoxane of (A) has less than 25 hydroxyl groups per 100aluminum atoms.
 55. A catalyst composition according to claim 53 whereinsaid hydroxyaluminoxane of (A) consists essentially ofhydroxyisobutylaluminoxane.
 56. A catalyst composition according toclaim 53 wherein said hydroxyaluminoxane of (A) is supported on aparticulate inorganic catalyst support material.
 57. A catalystcomposition according to claim 56 wherein said support material consistsessentially of a particulate porous silica pretreated with an aluminumalkyl.
 58. A process for the production of a supportedhydroxyaluminoxane which comprises bringing together (i) an aluminumalkyl having at least two carbon atoms in at least one alkyl groupthereof dissolved in an inert solvent, (ii) a water source, and (iii) acarrier material, under hydroxyaluminoxane-forming reaction conditions.59. A process according to claim 58 wherein said aluminum alkyl is atrialkylaluminum having at least two carbon atoms in each alkyl groupthereof.
 60. A process according to claim 59 wherein said water sourceconsists essentially of free water.
 61. A process according to claim 59wherein said water source consists essentially of a hydrated inorganicsalt or un-dehydrated silica.
 62. A process according to claim 59wherein said carrier material is a particulate inorganic catalystsupport material.
 63. A process according to claim 62 wherein saidsupport material is comprised of anhydrous or substantially anhydrousparticles of silica, silica-alumina, or alumina.
 64. A process accordingto claim 62 wherein said support material consists essentially of aparticulate porous calcined silica.
 65. A process according to claim 62wherein said support material consists essentially of a particulateporous silica pretreated with an aluminum alkyl.
 66. A process offorming an olefin polymerization catalyst, which method comprisesfeeding into a vessel (A) a hydroxyaluminoxane and (B) a d-block orf-block metal ompound having at least one leaving group on a d-block orf-block metal atom thereof, (A) and (B) being in proportions such thatan active olefin polymerization catalyst is formed.
 67. A processaccording to claim 66 wherein the hydroxyaluminoxane is fed in the formof (i) a solution formed from the hydroxyaluminoxane in an inert solventor in a liquid polymerizable olefinic monomer, or both; (ii) a slurryformed from the hydroxyaluminoxane in an inert diluent or in a liquidpolymerizable olefinic monomer, or both; (iii) unsupported solidparticles; (iv) one or more solids on a carrier material; or (v) anycombination of two or more of (i), (ii), (iii), and (iv).
 68. A processof forming an olefin polymerization catalyst, which method comprisesfeeding into a vessel (A) a hydroxyaluminoxane and (B) a d-block orf-block metal compound having at least one leaving group on a d-block orf-block metal atom thereof, wherein (A) and (B) are proportioned suchthat an active olefin polymerization catalyst is formed.
 69. A processaccording to claim 68 wherein the hydroxyaluminoxane is fed in the formof (i) a solution formed from the hydroxyaluminoxane and an inertsolvent or in a liquid polymerizable olefinic monomer, or both; (ii) aslurry formed from the hydroxyaluminoxane and an inert diluent or in aliquid polymerizable olefinic monomer, or both; (iii) unsupported solidparticles; (iv) one or more solids on a carrier material; or (v) anycombination of two or more of (i), (ii), (iii), and (iv).
 70. A processaccording to claim 69 wherein the hydroxyaluminoxane is fed in the formof (iv).
 71. A process according to claim 69 wherein the d- or f-blockmetal compound is fed in the form of (a) a solution or slurry of thed-block or f-block metal compound in an nert solvent or diluent, or in aliquid polymerizable olefinic monomer, or in a mixture of any of these,or (b) undiluted solids or liquid.
 72. A process according to claim 71wherein the hydroxyaluminoxane is fed in the form of (iv).
 73. A processaccording to any of claims 71 or 72 wherein the d-block or f-block metalcompound is fed in the form of (a).
 74. In a process for the catalyticpolymerization of at least one olefin in a reaction vessel or reactionzone, the improvement which comprises introducing into the reactionvessel or reaction zone catalyst components comprising (A) ahydroxyaluminoxane and (B) a d-block or f-block metal compound having atleast one leaving group on a d-block or f-block metal atom thereof, inproportions such that said at least one olefin is polymerized.
 75. Theimprovement according to claim 74 wherein the hydroxyaluminoxane isintroduced in the form of a solution formed from the hydroxyaluminoxanein an inert solvent or in a liquid form of said at least one olefin, orboth.
 76. The improvement according to claim 74 wherein thehydroxyaluminoxane is introduced in the form of a slurry formed from thehydroxyaluminoxane in an inert diluent or in a liquid form of said atleast one olefin.
 77. The improvement according to claim 74 wherein thehydroxyaluminoxane is introduced in the form of unsupported solidparticles.
 78. The improvement according to claim 74 wherein thehydroxyaluminoxane is introduced in the form of one or more solids on acarrier material.
 79. The improvement according to claim 74 wherein theone or more solids on the carrier material are in an inert viscousliquid.
 80. A process comprising (i) bringing together (a) an aluminumalkyl in which at least one alkyl group thereof has at least two carbonatoms, (b) a carrier material, and (c) an inert diluent which optionallyis or includes a solvent for the aluminum alkyl, to form a firstmixture, (ii) bringing together a water source and the first mixtureunder hydroxyaluminoxane-forming reaction conditions so as to form asecond mixture, and (iii) bringing together the second mixture and ad-block or f-block metal compound having at least one leaving group on ad-block or f-block metal atom thereof so as to form a third mixturecomprised of an activated polymerization catalyst supported by thecarrier material.
 81. A process according to claim 80 wherein thecarrier material is silica, and the aluminum alkyl is a trialkylaluminumin which each alkyl group contains at least two carbon atoms.
 82. Aprocess according to claim 80 further comprising recovering theactivated polymerization catalyst supported by the carrier material fromthe third mixture.
 83. A process according to claim 81 wherein saidd-block or f-block metal compound is a metallocene.
 84. A processaccording to claim 83 wherein said metallocene contains two bridged orunbridged cyclopentadienyl-moiety-containing groups.
 85. A processaccording to claim 84 wherein the d-block or f-block metal of saidmetallocene is a Group 4 metal.
 86. A process according to claim 85wherein said at least one leaving group of said metallocene is a methylgroup.
 87. A process according to claim 86 wherein said Group 4 metal iszirconium or hafnium.
 88. A process according to any of claims 80, 83,85, 86, or 87 wherein said carrier material consists essentially of aparticulate inorganic catalyst support material, and wherein said watersource is free water.